Wipe with a guanidinyl-containing polymer

ABSTRACT

A wipe article includes a substrate, a cationic coating disposed on a surface of the substrate, distributed throughout the substrate, or both. The cationic coating contains a guanidinyl-containing polymer that is crosslinked and bound to the substrate. The substrate includes sponge, nonwoven fabric, or woven fabric. The wipes are useful for removing microorganisms from a microorganism-contaminated surface and also for reducing re-contamination of the cleaned surface or transfer to another surface of the removed microorganisms.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.16/036,016, filed Jul. 16, 2018, which a divisional of U.S. Pat. No.10,087,405, issued Oct. 2, 2018, which is a national stage filing under35 U.S.C. 371 of PCT/US2014/043437, filed Jun. 20, 2014, which claimspriority to U.S. Application No. 61/840,537, filed Jun. 28, 2013, thedisclosure of which is incorporated by reference in its/their entiretyherein.

TECHNICAL FIELD

The present disclosure is directed to a wipe having a cationic coatingthat contains a guanidinyl-containing polymer. Methods of using the wipeand methods of making the wipe are also disclosed.

BACKGROUND

Microbial contamination can be a problem in many fields of activity.Unwanted microbial populations can be a health hazard, can causeproblems in pharmaceutical and food production, and can cause waste dueto the harmful effects of such bioactive microbial contamination onsensitive compositions and materials. Many surfaces can contain amicrobial residue of sufficiently high numbers to contaminate asensitive product or process. Elimination or removal of such microbialresidue is a desired end.

In the healthcare industry it is a common practice to clean and/ordisinfect environmental surfaces, medical instruments and devices toenhance hygiene and patient safety. Effective disinfection must actagainst a broad spectrum of microorganisms including those resistant tocommon antibacterial agents. However, some high level disinfectants usedfor the eradication of these resistant microorganisms are corrosive tomedical instruments and surfaces.

In the past, sponges, woven and nonwoven fabric and similar materialshave been used as wipes and have been combined with solvent or smallmolecule chemistry to obtain microbial removal and micro-biocidal orstatic growth characteristics. Although these wipes might all haveuseful physical attributes, a substantial need exists in the art toobtain removal of harmful microbial populations from surfaces, withlittle or no risk of re-contamination or re-deposition from the wipe.

SUMMARY

The present disclosure is directed to a wipe that contains a cationiccoating, to methods of making the wipe, and to methods of using thewipe. The cationic coating includes a guanidinyl-containing polymer thatis crosslinked, or that is covalently attached to the substrate, or bothcrosslinked and covalently attached to the substrate. The coating is noteasily separated from the substrate. As a result, minimal or no residueof the cationic coating is left on surfaces after being cleaned by thewipes.

The wipes are useful for removing microorganisms from amicroorganism-contaminated surface and also for reducingre-contamination of the cleaned surface with the removed microorganismor transfer of the removed microorganisms to another surface.Advantageously, when contacted with an area of amicroorganism-contaminated surface, the wipes can remove at least 99percent of the microorganisms in the area. The removed microorganismsare attached to the wipe and no more than 0.2 percent of the removedmicroorganisms are transferred from the wipe to a second surface whenthe wipes are contacted with a second surface or with the previouslycleaned surface.

In a first aspect, a wipe is provided that includes (a) a substratecomprising a sponge, a woven fabric, or a nonwoven fabric and (b) acationic coating disposed on a surface of the substrate, distributedthroughout at least a portion of the substrate, or both. The cationiccoating contains a guanidinyl-containing polymer that is crosslinked,covalently attached to the substrate, or both. When the wipe iscontacted in the presence of a liquid with an area of amicroorganism-contaminated surface, at least 99 percent ofmicroorganisms present on the microorganism-contaminated surface areremoved from the area by the wipe, and wherein the wipe, when contactedin the presence of the liquid with the area of themicroorganism-contaminated surface and then contacted with a secondsurface, transfers no more than 0.2 percent of the microorganisms fromthe wipe to the second surface.

In a second aspect, a method of removing microorganisms from amicroorganism-contaminated surface is provided. The method includespreparing a wipe that includes (a) a substrate comprising a sponge, awoven fabric, or a nonwoven fabric and (b) a cationic coating disposedon a surface of the substrate, distributed throughout at least a portionof the substrate, or both. The cationic coating contains aguanidinyl-containing polymer that is crosslinked, covalently attachedto the substrate, or both. The method further includes contacting thewipe in the presence of a liquid with an area of themicroorganism-contaminated surface, wherein at least 99 percent ofmicroorganisms present on the microorganism-contaminated surface areremoved from the area by the wipe, and wherein the wipe, when contactedin the presence of the liquid with the area of themicroorganism-contaminated surface and then contacted with a secondsurface, transfers no more than 0.2 percent of the microorganisms fromthe wipe to the second surface.

Other features and aspects of the wipes, methods of making the wipes,and methods of using the wipes are set forth in greater detail below.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1 to 3 are schematic profile views of exemplary wipes.

FIGS. 4A and 4B are schematic views of a mechanical wiping device usedin testing wipes of the present disclosure.

DETAILED DESCRIPTION

The coated wipe includes a substrate and a cationic coating bound to thesubstrate. The cationic coating includes a guanidinyl-containing polymerthat is crosslinked, covalently attached to the substrate, or both. Thewipe is useful, for example, for effective removal of such contaminantsas microorganisms from a microorganism-contaminated surface and forminimal transfer of the removed microorganisms to another surface or toa previously cleaned surface.

As used herein, “polymer” is inclusive of a homopolymer, copolymer,terpolymer, and the like.

As used herein, “(meth)acrylic” is inclusive of both methacrylic andacrylic. Likewise, the term “(meth)acrylamide” refers to bothmethacrylamide and acrylamide and the term “(meth)acrylate refers toboth methacrylate and acrylate.

As used herein, “wet-contacting” and “contacting in the presence of aliquid” are used interchangeable and generally refer to contacting awipe with a surface (e.g., a microorganism-contaminated surface such asa surface contaminated with microorganisms), wherein the wipe and/or thesurface is wet with a liquid at an area where the surface and the wipecome into contact with each other. The liquid typically includes atleast 10 weight percent water and can include up to 100 weight percentwater, relative to a total weight of the liquid.

As used herein, the term “bound” or “binding” in reference to thecationic coating (e.g., the guanidinyl-containing polymer in thecationic coating) being bound to the substrate or binding the cationiccoating to the substrate means that the cationic coating cannot beremoved without destroying the substrate. The cationic coating can bechemically attached to the substrate or can be crosslinked around thefibers of the substrate such that the coating cannot be removed bypeeling, dissolving in water or an organic solvent.

The term “microorganism” refers to bacteria (including gram-positivebacteria and gram-negative bacteria), fungi (e.g., yeasts), molds,protozoans, viruses (including both non-enveloped and envelopedviruses), bacterial endospores, and the like, and combinations thereof.In some embodiments, the microorganisms include bacterial endospores.

FIG. 1 is a schematic profile view of an exemplary embodiment of a wipe100 having a substrate 110 and a cationic coating layer 120 disposed ona surface of the substrate. FIG. 2 shows another exemplary embodiment ofa wipe 200 that includes a substrate 210 and a cationic coating layer220 disposed on a first major surface of substrate 210. Wipe 200 furtherincludes a coating layer 222 disposed on a second major surface ofsubstrate layer 210 opposite the first major surface of substrate 210.In some embodiments, coating layer 222 can include the same cationiccoating composition used in cationic coating layer 220, although this isnot a requirement, and coating layer 222 can alternatively include othercoating compositions. FIG. 3 shows an exemplary embodiment of a coatedwipe 300 having a cationic coating layer 320 surrounding a substrate310. The figures are not drawn to scale.

In some other embodiments (not shown), a cationic coating can bedisposed on a surface of a substrate, as well as being distributedthrough at least a portion of the substrate. That is, the cationiccoating can penetrate into the substrate. For example, if the substrateis a sponge, the cationic coating may be on a surface of substrate andcan be distributed throughout all or any portion of the substrate. Inother examples, if the substrate includes fiber, the cationic coatingcan surround the fibers or any portion of the fibers.

The cationic coating includes a guanidinyl-containing polymer. Theguanidinyl group can be located at any position in the polymer. In mostembodiments, the guanidinyl group is part of a pendant group attached tothe backbone of the polymer. In some embodiments, however, theguanidinyl group is part of backbone of the polymer. As used herein, theterm “guanidinyl” refers to a group of the formula

—NR³—C(═NR⁴)—NR⁴R⁵. If the guanidinyl group is part of a pendant group,the group R³ refers to hydrogen, C₁-C₁₂ (hetero)alkyl, or C₅-C₁₂(hetero)aryl. If the guanidinyl group is part of the backbone of thepolymer, the group R³ can refer to a residue of a polymer chain. Eachgroup R⁴ is independently hydrogen, C₁-C₁₂ (hetero)alkyl, or C₅-C₁₂(hetero)aryl. Group R⁵ is hydrogen, C₁-C₁₂ (hetero)alkyl, C₅-C₁₂(hetero)aryl, or a group of formula —N(R⁴)₂. The guanidinyl group can bepart of a biguanidinyl group that is of formula—NR³—C(═NR⁴)—NR⁴—C(═NR⁴)—NR⁴R⁵ where the groups R³, R⁴, and R⁵ are thesame as defined above.

As used herein, “alkyl” refers to a monovalent radical of an alkane andincludes straight-chained, branched, and cyclic alkyl groups andincludes both unsubstituted and substituted alkyl groups. Unlessotherwise indicated, the alkyl groups typically contain from 1 to 20carbon atoms. Examples of “alkyl” as used herein include, but are notlimited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl,t-butyl, isopropyl, n-octyl, n-heptyl, ethylhexyl, cyclopentyl,cyclohexyl, cycloheptyl, adamantyl, and norbornyl, and the like.

As used herein, “alkylene” refers to a divalent radical of an alkane andincludes straight-chained, branched, and cyclic alkyl groups andincludes both unsubstituted and substituted alkyl groups. Unlessotherwise indicated, the alkyl groups typically contain from 1 to 20carbon atoms. Examples of “alkyl” as used herein include, but are notlimited to, methylene, ethylene, n-propylene, n-butylene, n-pentylene,isobutylene, t-butylene, isopropylene, n-octylene, n-heptylene,ethylhexylene, cyclopentylene, cyclohexylene, cycloheptylene,adamantylene, and norbomylene, and the like.

As used herein, “aryl” is a monovalent radical of an aromatic groupcontaining 5-12 ring atoms and can contain optional fused rings, whichmay be saturated, unsaturated, or aromatic. Examples of an aryl groupsthat are carbocylic include phenyl, naphthyl, biphenyl, phenanthryl, andanthracyl. The term “heteroaryl” refers to an aryl containing 1-3heteroatoms such as nitrogen, oxygen, or sulfur and can contain fusedrings. Some examples of heteroaryl groups are pyridyl, furanyl,pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, indolyl,benzofuranyl, and benzthiazolyl. The term “(hetero)aryl” refers to botharyl and heteroaryl groups.

As used herein, “arylene” is a divalent radical of an aromatic groupcontaining 5-12 ring atoms and can contain optional fused rings, whichmay be saturated, unsaturated, or aromatic. Examples of an arylenegroups that are carbocylic include phenylene, naphthylene, biphenylene,phenanthrylene, and anthracylene. The term “heteroarylene” refers to anarylene containing 1-3 heteroatoms such as nitrogen, oxygen, or sulfurand can contain fused rings. Some examples of heteroarylene groups arepyridylene, furanylene, pyrrolylene, thienylene, thiazolylene,oxazolylene, imidazolylene, indolylene, benzofuranylene, andbenzthiazolylene. The term “(hetero)arylene” refers to both arylene andheteroarylene.

Although any guanidinyl-containing polymer can be used in the cationiccoating, this polymer is often of Formula (I).

In Formula (I), the group R¹ is hydrogen, C₁-C₁₂ (hetero)alkyl, orC₅-C₁₂ (hetero)aryl, or a residue of the polymer chain. The group R² isa covalent bond, a C₂-C₁₂ (hetero)alkylene, or a C₅-C₁₂ (hetero)arylene.The group R³ is H, C₁-C₁₂ (hetero)alkyl, or C₅-C₁₂ (hetero)aryl, or canbe a residue of the polymer chain when n is 0. Each group R⁴ isindependently hydrogen, C₁-C₁₂ (hetero)alkyl, or C₅-C₁₂ (hetero)aryl.The group R⁵ is hydrogen, C₁-C₁₂ (hetero)alkyl, C₅-C₁₂ (hetero)aryl, or—N(R⁴)₂. The variable n is equal to 0 or 1 depending on the precursorpolymer used to form the guanidinyl-containing polymer. The variable mis equal to 1 or 2 depending on whether the cationic group is aguanidinyl or biguanidinyl group. The term “Polymer” in Formula (I)refers to all portions of the guanidinyl-containing polymer except the xgroups of formula —[C(R¹)═N—R²-]_(n)N(R³)—[C(═NR⁴)—NR⁴R⁵-]_(m). The termx is a variable equal to at least 1.

Most guanidinyl-containing polymers have more than one guanidinyl group.The number of guanidinyl groups can be varied depending the method usedto prepare the guanidinyl-containing polymer. For example, the number ofguanidinyl groups can depend on the choice of precursor polymer selectedfor reacting with a suitable guanylating agent. In some embodiments, thevariable x can be up to 1000, up to 500, up to 100, up to 80, up to 60,up to 40, up to 20, or up to 10.

The guanidinyl-containing polymer of Formula (I) is often the reactionproduct of (a) a precursor polymer and (b) a suitable guanylating agent.The precursor polymer is often an amino-containing polymer or acarbonyl-containing polymer. When the precursor polymer is anamino-containing polymer, the variable n in Formula (I) is typicallyequal to 0. When the precursor polymer is a carbonyl-containing polymer,the variable n is equal to 1. If the guanylating agent contains aguanidinyl group or a precursor of a guanidinyl group, the variable minFormula (I) is equal to 1. If the guanylating agent contains abiguanidinyl group or a precursor of a biguanidinyl group, the variablemin Formula (I) is equal to 2.

In embodiments where n is 0, the base polymer of theguanidinyl-containing polymer is often prepared by reaction of asuitable guanylating agent and an amino-containing polymer. In otherembodiments, where n is 1, the guanidinyl-containing polymer is oftenprepared by reaction of a suitable guanylating agent and acarbonyl-containing polymer.

In those embodiments where n is 0 and the precursor polymer is anamino-containing polymer, the structure of the guanidinyl-containingpolymer of Formula (I) can also be written more simply as the structureof Formula (II).

In Formula (II), the group R³ is hydrogen, C₁-C₁₂ (hetero)alkyl, orC₅-C₁₂ (hetero)aryl, or can be a residue of the polymer chain. When theguanidinyl group is part of a pendant group, R³ is hydrogen, C₁-C₁₂(hetero)alkyl, or C₅-C₁₂ (hetero)aryl. Each R⁴ is independentlyhydrogen, C₁-C₁₂ (hetero)alkyl, or C₅-C₁₂ (hetero)aryl. The group R⁵ ishydrogen, C₁-C₁₂ (hetero)alkyl, or C₅-C₁₂ (hetero)aryl, or—N(R⁴)₂. The variable m is equal to 1 or 2. The term “Polymer” inFormula (II) refers to all portions of the guanidinyl-containing polymerexcept the x groups of formula —N(R³)—[C(═NR⁴)—NR⁴R⁵-]_(m). The term xis a variable equal to at least 1.

The amino-containing polymer used as a precursor polymer to prepare aguanidinyl-containing polymer of Formula (II) can be represented by theformula Polymer-N(R³)H. As noted above, however, the amino-containingpolymer typically has many groups —N(R³)H but Formula (I) shows only onefor ease of discussion purposes only. The —N(R³)H groups can be aprimary or secondary amino group and can be part of a pendant group orpart of the backbone of the precursor polymer. The amino-containingpolymers can be synthesized or can be naturally occurring biopolymers.Suitable amino-containing polymers can be prepared by chain growth orstep growth polymerization procedures with amino-containing monomers.These monomers can also, if desired, be copolymerized with othermonomers without an amino-containing group. Additionally, theamino-containing polymers can be obtained by grafting primary orsecondary amine groups using an appropriate grafting technique.

In some embodiments, useful amino-containing polymers are polyaminesthat are water soluble or water-dispersible. As used herein, the term“water soluble” refers to a material that can be dissolved in water. Thesolubility is typically at least about 0.1 gram per milliliter of water.As used herein, the term “water dispersible” refers to a material thatis not water soluble but that can be emulsified or suspended in water.

Examples of amino-containing polymers suitable for use, which areprepared by chain growth polymerization include, but are not limited to,polyvinylamine, poly(N-methylvinylamine), polyallylamine,polyallylmethylamine, polydiallylamine, poly(4-aminomethylstyrene),poly(4-aminostyrene), poly(acrylamide-co-methylaminopropylacrylamide),and poly(acrylamide-co-aminoethylmethacrylate).

Examples of amino polymers suitable for use, which are prepared by stepgrowth polymerization include, but are not limited to, polyethylenimine,polypropylenimine, polylysine, polyaminoamides,polydimethylamine-epichlorohydrin-ethylenediamine, and any of a numberof polyaminosiloxanes, which can be prepared from monomers such asaminopropyltriethoxysilane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,N-trimethoxysilylpropyl-N-methylamine, andbis(trimethoxysilylpropyl)amine.

Other useful amino-containing polymers that have primary or secondaryamino end groups include, but are not limited to, dendrimers(hyperbranched polymers) formed from polyamidoamine (PAMAM) andpolypropylenimine. Exemplary dendrimeric materials formed from PAMAM arecommercially available under the trade designation “STARBURST (PAMAM)dendrimer” (e.g., Generation 0 with 4 primary amino groups, Generation 1with 8 primary amino groups, Generation 2 with 16 primary amino groups,Generation 3 with 32 primary amino groups, and Generation 4 with 64primary amino groups) from Aldrich Chemical (Milwaukee, Wis.).Dendrimeric materials formed from polypropylenimine are commerciallyavailable under the trade designation “DAB-Am” from Aldrich Chemical.For example, DAB-Am-4 is a generation 1 polypropylenimine tetraaminedendrimer with 4 primary amino groups, DAB-Am-8 is a generation 2polypropylenimine octaamine dendrimer with 8 primary amino groups,DAB-Am-16 is a generation 3 polypropylenimine hexadecaamine with 16primary amino groups, DAB-Am-32 is a generation 4 polypropyleniminedotriacontaamine dendrimer with 32 primary amino groups, and DAB-Am-64is a generation 5 polypropylenimine tetrahexacontaamine dendrimer with64 primary amino groups.

Examples of suitable amino-containing polymers that are biopolymersinclude chitosan as well as starch that is grafted with reagents such asmethylaminoethylchloride.

Still other examples of amino-containing polymers include polyacrylamidehomo- or copolymers and amino-containing polyacrylate homo- orcopolymers prepared with a monomer composition containing anamino-containing monomer such as an aminoalkyl(meth)acrylate,(meth)acrylamidoalkylamine, and diallylamine.

For some wipes, the preferred amino-containing polymers includepolyaminoamides, polyethyleneimine, polyvinylamine, polyallylamine, andpolydiallylamine.

Suitable commercially available amino-containing polymers include, butare not limited to, polyamidoamines that are available under the tradedesignations ANQUAMINE (e.g., ANQUAMINE 360, 401, 419, 456, and 701)from Air Products and Chemicals (Allentown, Pa.), polyethyleniminepolymers that are available under the trade designation LUPASOL (e.g.,LUPASOL FG, PR 8515, Waterfree, P, and PS) from BASF Corporation(Resselaer, N.Y.), polyethylenimine polymers such as those availableunder the trade designation CORCAT P-600 from EIT Company (Lake Wylie,S.C.), and polyamide resins such as those available from CognisCorporation (Cincinnati, Ohio) under the traded designation VERSAMIDseries of resins that are formed by reacting a dimerized unsaturatedfatty acid with alkylene polyamines.

Guanidinyl-containing polymers can be prepared by reaction of theamino-containing polymer precursor with a guanylating agent. Althoughall the amino groups of the amino-containing polymer can be reacted withthe guanylating agent, there are often some unreacted amino groups fromthe amino-containing polymer precursor remaining in theguanidinyl-containing polymer. Typically, at least 0.1 mole percent, atleast 0.5 mole percent, at least 1 mole percent, at least 2 molepercent, at least 10 mole percent, at least 20 mole percent, or at least50 mole percent of the amino groups in the amino-containing polymerprecursor are reacted with the guanylating agent. Up to 100 molepercent, up to 90 mole percent, up to 80 mole percent, or up to 60 molepercent of the amino groups can be reacted with the guanylating agent.For example, the guanylating agent can be used in amounts sufficient tofunctionalize 0.1 to 100 mole percent, 0.5 to 90 mole percent, 1 to 90mole percent, 1 to 80 mole percent, 1 to 60 mole percent, 2 to 50 molepercent, 2 to 25 mole percent, or 2 to 10 mole percent of the aminogroups in the amino-containing polymer.

Known guanylating agents for reaction with an amino-containing polymerprecursor include, but are not limited to, cyanamide; O-alkylisoureasalts such as O-methylisourea sulfate, O-methylisourea hydrogen sulfate,O-methylisourea acetate, O-ethylisourea hydrogen sulfate, andO-ethylisourea hydrochloride; chloroformamidine hydrochloride;1-amidino-1,2,4-triazole hydrochloride;3,5-dimethylpyrazole-1-carboxamidine nitrate; pyrazole-1-carboxamidinehydrochloride; N-amidinopyrazole-1-carboxamidine hydrochloride; andcarbodiimides such as dicyclohexylcarbodiimide,N-ethyl-N′-(3-dimethylaminopropyl)carbodiimide, anddiisopropylcarbodiimide. The amino-containing polymer may also beacylated with guanidino-functional carboxylic acids such asguanidinoacetic acid and 4-guanidinobutyric acid in the presence ofactivating agents such as EDC(N-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride), or EEDQ(2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline). Additionally, theguanidinyl-containing polymer may be prepared by alkylation withchloroacetone guanyl hydrazone, as described in U.S. Pat. No. 5,712,027(Ali et al.).

Guanylating agents for the preparation of biguanide-containing polymersinclude sodium dicyanamide, dicyanodiamide and substitutedcyanoguanidines such as N³-p-chlorophenyl-N1-cyanoguanidine,N³-phenyl-N¹-cyanoguanidine, N³-alpha-naphthyl-N¹-cyanoguanidine,N³-methyl-N1-cyanoguanidine, N³,N³-dimethyl-N¹-cyanoguanidine,N³-(2-hydroxyethyl)-N¹-cyanoguanidine, and N³-butyl-N¹-cyanoguanidine.Alkylene- and arylenebiscyanoguanidines may be utilized to preparebiguanide functional polymers by chain extension reactions. Thepreparation of cyanoguanidines and biscyanoguanidines is described indetail in Rose, F. L. and Swain, G. J. Chem Soc., 1956, pp. 4422-4425.Other useful guanylating reagents are described by Alan R. Katritzky etal., Comprehensive Organic Functional Group Transformation, Vol. 6, p.640.

The guanidinyl-containing polymer formed by reaction of anamino-containing polymer precursor and a guanylating agent will havependent or catenary guanidinyl groups of the Formula (III).

In Formula (III), the groups R³, R⁴, and R⁵ and the variable m are thesame as defined above. The wavy line attached to the N(R³) group showsthe position of attachment the group to the rest of the polymericmaterial. In most embodiments, the group of Formula (III) is in apendant group of the guanidinyl-containing polymer.

In some embodiments, it may be advantageous to react theamino-containing polymer precursor to provide other ligands or groups inaddition to the guanidinyl-containing group. For example, it may beuseful to include a hydrophobic ligand, an ionic ligand, or a hydrogenbonding ligand. This can be particularly advantageous for the removal ofcertain microorganisms during the wiping of a microorganism-contaminatedsurface.

The additional ligands can be readily incorporated into theamino-containing polymers by alkylation or acylation procedures wellknown in the art. For example amino groups of the amino-containingpolymer can be reacted using halide, sulfonate, and sulfate displacementreactions or using epoxide ring opening reactions. Useful alkylatingagents for these reactions include, for example, dimethylsulfate, butylbromide, butyl chloride, benzyl bromide, dodecyl bromide,2-chloroethanol, bromoacetic acid, 2-chloroethyltrimethylammoniumchloride, styrene oxide, glycidyl hexadecyl ether,glycidyltrimethylammonium chloride, and glycidyl phenyl ether. Usefulacylating agents include, for example, acid chlorides and anhydridessuch as benzoyl chloride, acetic anhydride, succinic anhydride, anddecanoyl chloride, and isocyanates such as trimethylsilylisocyanate,phenyl isocyanate, butyl isocyanate, and butyl isothiocyanate. In suchembodiments 0.1 to 20 mole percent, preferably 2 to 10 mole percent, ofthe available amino groups of the amino-containing polymer may bealkylated and/or acylated.

The guanidinyl-containing polymer can be crosslinked. Theamino-containing polymer can be crosslinked prior to reaction with theguanylating agent. Alternatively, the guanidinyl-containing polymer canbe crosslined by reaction of a crosslinker with remaining amino groupsfrom the amino-containing polymer precursor or with some of theguanidinyl groups. Suitable crosslinkers include amine-reactivecompounds such as bis- and polyaldehydes such as glutaraldehyde, bis-and polygylcidylethers such as butanedioldiglycidylether andethyleneglycoldiglycidylether, polycarboxylic acids and theirderivatives (e.g., acid chlorides), polyisocyanates, formaldehyde-basedcrosslinkers such as hydroxymethyl and alkoxymethyl functionalcrosslinkers, such as those derived from urea or melamine, andamine-reactive silanes, such as 3-glycidoxypropyltrimethoxysilane,3-glycidoxypropyltriethoxysilane, 5,6-epoxyhexyltriethoxysilane,(p-chloromethyl)phenyltrimethoxysilane, chloromethyltriethoxysilane,3-isocyanatopropyltriethoxysilane, and3-thiocyanatopropyltriethoxysilane.

In other embodiments, the guanidinyl-containing polymer is of Formula(IV), which corresponds to Formula (I) where n is equal to 1.

In Formula (IV), the group R¹ is hydrogen, C₁-C₁₂ (hetero)alkyl, orC₅-C₁₂ (hetero)aryl, or a residue of the polymer chain. If theguanidinyl-containing group is the reaction product of a guanylatingagent and a carbonyl group that is part of the backbone of the polymer,R¹ is a residue of the polymer chain. Group R² is a covalent bond, aC₂-C₁₂ (hetero)alkylene, or a C₅-C₁₂ (hetero)arylene. Group R³ ishydrogen, C₁-C₁₂ (hetero)alkyl, or C₅-C₁₂ (hetero)aryl. Each R⁴ isindependently H, C₁-C₁₂ (hetero)alkyl, or C₅-C₁₂ (hetero)aryl. Group R⁵is hydrogen, C₁-C₁₂ (hetero)alkyl, or C₅-C₁₂ (hetero)aryl, or —N(R⁴)₂.The variable m is equal to 1 or 2. The term “Polymer” in Formula (I)refers to all portions of the guanidinyl-containing polymer except the xgroups of formula —C(R¹)═N—R²—N(R³)—[C(═NR⁴)—NR⁴R⁵-]_(m). The term x isa variable equal to at least 1.

Guanidinyl-containing polymers of Formula (IV) are the reaction productof a carbonyl-containing polymer and a suitable guanylating agent forreaction with a carbonyl group. The carbonyl-containing polymer used asa precursor polymer to prepare a guanidinyl-containing polymer ofFormula (IV) can be represented by the formula Polymer-C(O)—R¹. Thecarbonyl-containing polymer precursor typically has many groups —C(O)—R¹but Formula (IV) shows only one for ease of discussion purposes only.The carbonyl group —C(O)—R¹ is an aldehyde group (when R¹ is hydrogen)or a ketone groups (when R¹ ia a (hetero)alkyl or (hetero)aryl).Although the carbonyl-group can be part of the polymeric backbone orpart of a pendant group from the polymeric backbone, it is typically ina pendant group.

In some embodiments, the carbonyl-containing polymer is the polymerizedproduct of a monomer composition that includes an ethylenicallyunsaturated monomer having a carbonyl group, preferably a ketone group.Suitable monomers having a carbonyl group include, but are not limitedto, acrolein, vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutylketone, isopropenyl methyl ketone, vinyl phenyl ketone, diacetone(meth)acrylamide, acetonyl acrylate, andacetoacetoxyethyl(meth)acrylate.

In other embodiments, the carbonyl-containing polymer is the polymerizedproduct of a monomer composition that includes carbon monoxide and oneor more ethylenically unsaturated monomer (i.e., the carbonyl-containingpolymer is a carbon monoxide copolymers). An example of a carbonmonoxide containing copolymer is ELVALOY 741, a terpolymer ofethylene/vinyl acetate/carbon monoxide from DuPont (Wilmington, Del.,USA).

In addition to carbon monoxide and/or an ethylenically unsaturatedmonomer with a carbonyl group (e.g., a ketone group), the monomercomposition used to form that carbonyl-containing polymer can optionallyfurther comprise ethylenically unsaturated hydrophilic monomer units. Asused herein, “hydrophilic monomers” are those polymerizable monomershaving water miscibility (water in monomer) of at least 1 weight percentpreferably at least 5 weight percent without reaching a cloud point, andcontain no functional groups that would interfere with the binding ofbiological substances to the ligand group. The carbonyl-containingpolymer may include, for example, 0 to 90 weight percent of thehydrophilic monomers in the monomer composition. If present, thehydrophilic monomer can be present in an amount in a range of 1 to 90weight percent, 1 to 75 weight percent, 1 to 50 weight percent, 1 to 25weight percent, or 1 to 10 weight percent based on based a total weightof the monomer composition.

The hydrophilic groups of the hydrophilic monomers may be neutral, havea positive charge, a negative charge, or a combination thereof.Hydrophilic monomers with an ionic group can be neutral or chargeddepending on the pH conditions. Hydrophilic monomers are typically usedto impart a desired hydrophilicity (i.e. water solubility ordispersibility) to the carbonyl-containing polymer. A negatively chargedhydrophilic monomer may be included as long as it is in small enoughamounts that it doesn't interfere with the binding interaction of theguanidinyl group.

Some exemplary hydrophilic monomers that are capable of providing apositive charge are amino (meth)acrylates or amino (meth)acrylamides ofFormula (V) or quaternary ammonium salts thereof. The counter ions ofthe quaternary ammonium salts are often halides, sulfates, phosphates,nitrates, and the like.

In Formula (V), the group X is oxy (i.e., —O—) or —NR³— where R³ ishydrogen, C₁-C₁₂ (hetero)alkyl, or C₅-C₁₂ (hetero)aryl. The group R⁶ isa C₂ to C₁₀ alkylene, preferably a C₂-C₆ alkylene. The group R⁷ isindependently hydrogen or methyl. Each R⁸ is independently hydrogen,alkyl, hydroxyalkyl (i.e., an alkyl substituted with a hydroxy), oraminoalkyl (i.e., an alkyl substituted with an amino). Alternatively,the two R⁸ groups taken together with the nitrogen atom to which theyare attached can form a heterocyclic group that is aromatic, partiallyunsaturated (i.e., unsaturated but not aromatic), or saturated, whereinthe heterocyclic group can optionally be fused to a second ring that isaromatic (e.g., benzene), partially unsaturated (e.g., cyclohexene), orsaturated (e.g., cyclohexane).

It will be understood with respect to Formula (V) that the depictedethylenically unsaturated (meth)acryloyl group (CH₂═C(R⁷)—C(O)— group)may be replaced by another ethylenically unsaturated group of reducedreactivity, such as vinyl, vinyloxy, allyl, allyloxy, and acetylenyl.

In some embodiments of Formula (V), both R⁸ groups are hydrogen. Inother embodiments, one R⁸ group is hydrogen and the other is an alkylhaving 1 to 10, 1 to 6, or 1 to 4 carbon atoms. In still otherembodiments, at least one of R⁸ groups is a hydroxy alkyl or an aminoalkyl that have 1 to 10, 1 to 6, or 1 to 4 carbon atoms with the hydroxyor amino group being positioned on any of the carbon atoms of the alkylgroup. In yet other embodiments, the R⁸ groups combine with the nitrogenatom to which they are attached to form a heterocyclic group. Theheterocyclic group includes at least one nitrogen atom and can containother heteroatoms such as oxygen or sulfur. Exemplary heterocyclicgroups include, but are not limited to imidazolyl. The heterocyclicgroup can be fused to an additional ring such as a benzene, cyclohexene,or cyclohexane. Exemplary heterocyclic groups fused to an additionalring include, but are not limited to, benzoimidazolyl.

Exemplary amino acrylates (i.e., “X” in Formula (V) is oxy) includeN,N-dialkylaminoalkyl (meth)acrylates such as, for example,N,N-dimethylaminoethyl(meth)acrylate, N,N-dimethylaminoethylacrylate,N,N-diethylaminoethylacrylate, N,N-dimethylaminopropyl(meth)acrylate,N-tert-butylaminopropyl(meth)acrylate, and the like.

Exemplary amino (meth)acrylamides (i.e., “X” in Formula (V) is —NR³—)include, for example, N-(3-aminopropyl)methacrylamide,N-(3-aminopropyl)acrylamide, N-[3-(dimethylamino)propyl]methacrylamide,N-[3-(dimethylamino)propyl]acrylamide,N-(3-imidazolylpropyl)methacrylamide, N-(3-imidazolylpropyl)acrylamide,N-(2-imidazolylethyl)methacrylamide,N-(1,1-dimethyl-3-imidazolylpropyl)methacrylamide,N-(1,1-dimethyl-3-imidazolylpropyl)acrylamide,N-(3-benzimidazolylpropyl)acrylamide, andN-(3-benzimidazolylpropyl)methacrylamide.

Exemplary quaternary salts of the monomers of Formula (V) include, butare not limited to, (meth)acrylamidoalkyltrimethylammonium salts (e.g.,3-methacrylamidopropyltrimethylammonium chloride and3-acrylamidopropyltrimethylammonium chloride) and(meth)acryloxyalkyltrimethylammonium salts (e.g.,2-acryloxyethyltrimethylammoniumchloride,2-methacryloxyethyltrimethylammoniumchloride,3-methacryloxy-2-hydroxypropyltrimethylammonium chloride,3-acryloxy-2-hydroxypropyltrimethylammonium chloride, and2-acryloxyethyltrimethylammonium methyl sulfate).

Other monomers that can provide positively charged groups to the polymerinclude the dialkylaminoalkylamine adducts of alkenylazlactones (e.g.,2-(diethylamino)ethylamine, (2-aminoethyl)trimethylammonium chloride,and 3-(dimethylamino)propylamine adducts of vinyldimethylazlactone) anddiallylamine monomers (e.g., diallylammonium chloride anddiallyldimethylammoniumchloride).

In some preferred embodiments, the optional hydrophilic monomer may havean ethylenically unsaturated group such as a (meth)acryloyl group and apoly(alkylene oxide) group. For example, the hydrophilic monomer can bea poly(alkylene oxide) mono(meth)acrylate compounds, where the terminusis a hydroxy group, or an alkyl ether group. Such monomers are of thegeneral Formula (VI).

R⁹—O—(CH(R⁹)—CH₂—O)_(p)—C(O)—C(R⁹)═CH₂  (VI)

In Formula (VI), each R⁹ is independently hydrogen or a C₁-C₄ alkyl. Thevariable p is at least 2 such as, for example, 2 to 100, 2 to 50, 2 to20, or 2 to 10.

In one embodiment, the poly(alkylene oxide) group (depicted as—(CH(R⁹)—CH2-O)_(p)—) is a poly(ethylene oxide). In another embodiment,the poly(alkylene oxide) group is a poly(ethylene oxide-co-propyleneoxide). Such copolymers may be block copolymers, random copolymers, orgradient copolymers.

Other representative examples of suitable hydrophilic monomers includebut are not limited to acrylic acid; methacrylic acid;2-acrylamido-2-methyl-1-propanesulfonic acid; 2-hydroxyethyl(meth)acrylate; N-vinylpyrrolidone; N-vinylcaprolactam; acrylamide;mono- or di-N-alkyl substituted acrylamide; t-butyl acrylamide;dimethylacrylamide; N-octyl acrylamide; poly(alkoxyalkyl)(meth)acrylates including 2-(2-ethoxyethoxy)ethyl (meth)acrylate,2-ethoxyethyl (meth)acrylate, 2-methoxyethoxyethyl (meth)acrylate,2-methoxyethyl methacrylate, polyethylene glycol mono(meth)acrylates;alkyl vinyl ethers, including vinyl methyl ether; and mixtures thereof.Preferred hydrophilic monomers include those selected from the groupconsisting of dimethylacrylamide, 2-hydroxyethyl (meth)acrylate, andN-vinylpyrrolidinone.

In some embodiments, the monomer composition used to form thecarbonyl-containing polymer can optionally include a hydrophobicmonomer. As used herein, the term “hydrophobic monomer” refers monomershaving a water miscibility (water in monomer) that is less than 1 weightpercent. The hydrophobic monomers can be used in amounts that do notdeleteriously affect the binding performance of theguanidinyl-containing monomer polymer and/or the water dispersibility ofthe guanidinyl-containing polymer. When present, the hydrophobic monomeris typically present in an amount in a range of 1 to 20 weight percent,1 to 10 weight percent, or 1 to 5 weight percent based on a total weightof monomers in the monomer composition.

Useful classes of hydrophobic monomers include alkyl acrylate esters andamides, exemplified by straight-chain, cyclic, and branched-chainisomers of alkyl esters containing C₁-C₃₀ alkyl groups and mono- ordialkyl acrylamides containing C₁-C₃₀ alkyl groups. Useful specificexamples of alkyl acrylate esters include: methyl acrylate, ethylacrylate, n-propyl acrylate, n-butyl acrylate, iso-amyl acrylate,n-hexyl acrylate, n-heptyl acrylate, isobornyl acrylate, n-octylacrylate, iso-octyl acrylate, 2-ethylhexyl acrylate, iso-nonyl acrylate,decyl acrylate, undecyl acrylate, dodecyl acrylate, lauryl acrylate,tridecyl acrylate, and tetradecyl acrylate. Useful specific examples ofalkyl acrylamides include mono- and diacrylamides having pentyl, hexyl,heptyl, isobornyl, octyl, 2-ethylhexyl, iso-nonyl, decyl, undecyl,dodecyl, tridecyl, and tetradecyl groups may be used. The correspondingmethacrylate esters may be used.

Additional useful classes of hydrophobic monomers further include vinylmonomers such as vinyl acetate, styrenes, and alkyl vinyl ethers, andmaleic anhydride.

The monomer composition used to form the carbonyl-containing polymer istypically combined with a free radical initiator to form the polymerizedproduct. Any suitable free radical initiator can be used. The initiatoris typically present in an amount in the range of 0.01 to 5 weightpercent, in the range of 0.01 to 2 weight percent, in the range of 0.01to 1 weight percent, or in the range of 0.01 to 0.5 weight percent basedon a total weight of monomers in the monomer composition.

In some embodiments, a thermal initiator is used. Thermal initiators canbe water-soluble or water-insoluble (i.e., oil-soluble) depending on theparticular polymerization method used. Suitable water-soluble initiatorsinclude, but are not limited to, persulfates such as potassiumpersulfate, ammonium persulfate, sodium persulfate, and mixturesthereof; an oxidation-reduction initiator such as the reaction productof a persulfate and a reducing agent such as a metabisulfite (e.g.,sodium metabisulfite) or a bisulfate (e.g., sodium bisulfate); or4,4′-azobis(4-cyanopentanoic acid) and its soluble salts (e.g., sodiumor potassium). Suitable oil-soluble initiators include, but are notlimited to, various azo compound such as those commercially availableunder the trade designation VAZO from DuPont (Wilmington, Del., USA)including VAZO 67, which is 2,2′-azobis(2-methylbutane nitrile), VAZO64, which is 2,2′-azobis(isobutyronitrile), and VAZO 52, which is(2,2′-azobis(2,4-dimethylpentanenitrile); and various peroxides such asbenzoyl peroxide, cyclohexane peroxide, lauroyl peroxide, and mixturesthereof.

In many embodiments, a photoinitiator is used. Some exemplaryphotoinitiators are benzoin ethers (e.g., benzoin methyl ether orbenzoin isopropyl ether) or substituted benzoin ethers (e.g., anisoinmethyl ether). Other exemplary photoinitiators are substitutedacetophenones such as 2,2-diethoxyacetophenone or2,2-dimethoxy-2-phenylacetophenone (commercially available under thetrade designation IRGACURE 651 from BASF Corp. (Florham Park, N.J., USA)or under the trade designation ESACURE KB-1 from Sartomer (Exton, Pa.,USA)). Still other exemplary photoinitiators are substitutedalpha-ketols such as 2-methyl-2-hydroxypropiophenone, aromatic sulfonylchlorides such as 2-naphthalenesulfonyl chloride, and photoactive oximessuch as 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime. Othersuitable photoinitiators include, for example, 1-hydroxycyclohexylphenyl ketone (IRGACURE 184),bis(2,4,6-trimethylbenzoyl)phenylphosphineoxide (IRGACURE 819),1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one(IRGACURE 2959), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone(IRGACURE 369),2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (IRGACURE907), and 2-hydroxy-2-methyl-1-phenyl propan-1-one (DAROCUR 1173).

The guanidinyl-containing polymers according to Formula (IV) are oftenthe reaction product of a carbonyl-containing polymer precursor and aguanylating agent of Formula (VII).

In Formula (VII), the group R² is a covalent bond, C₂-C₁₂(hetero)alkylene, or C₅-C₁₂ (hetero)arylene. Group R³ is hydrogen,C₁-C₁₂ (hetero)alkyl, or C₅-C₁₂ (hetero)aryl. Each R⁴ is independentlyhydrogen, C₁-C₁₂ (hetero)alkyl, or C₅-C₁₂ (hetero)aryl. Group R⁵ is H,C₁-C₁₂ (hetero)alkyl, or C₅-C₁₂ (hetero)aryl, or —N(R⁴)₂. The variable mis equal to 1 or 2.

For ease of description, the carbonyl-containing polymer can berepresented by the formula Polymer-C(═O)—R¹. The carbonyl group can bein the backbone or in a pendant group but is usually in a pendant group.When reacted with a guanylating agent of Formula (VII), the carbonylgroup in the carbonyl-containing polymer undergoes a condensationreaction with a terminal amine group of the guanylating agent. Theguanidinyl-containing polymer typically has guanidinyl-containingpendant groups of Formula (VIII).

The groups R², R³, R⁴, and R⁵ are the same as described above forFormula (VII). The group of formula

in Formula (VIII) is the linkage formed between the terminal amine ofthe ligand compound of Formula (VII) and the carbonyl group of thecarbonyl-containing polymer. The wavy line denotes the attachment siteof the group via a covalent bond to the rest of the polymer. Group R¹ ishydrogen (when the carbonyl group is an aldehyde group), C₁-C₁₂(hetero)alkyl (when the carbonyl group is a ketone group and the ketonegroup is part of a pendant group), or C₅-C₁₂ (hetero)aryl (when thecarbonyl group is a ketone group and the ketone group is part of apendant group), or a residue of the polymer chain (when the carbonylgroup is a group in the backone of the carbonyl-containing polymer). Inmost embodiments, the group of Formula (VIII) is part of a pendant groupof the guanidinyl-containing polymer.

In other embodiments, the guanidyl-containing polymer may be prepared inwhich the imine linking group (˜˜C(R¹)═N—) is reduced to an aminelinking group (˜˜C(R¹)—NH—). This may be effected by treating the extantligand functional polymer with a reducing agent, such as sodiumcyanoborohydride, or the reduction may be effected in situ by adding thereducing agent to the reaction mixture of the carbonyl functional(co)polymer and the compound of Formula V.

In many embodiments, some but not all of the carbonyl groups of thecarbonyl-containing polymer are reacted with the guanylating agent ofFormula (VII). Typically, at least 0.1 mole percent, at least 0.5 molepercent, at least 1 mole percent, at least 2 mole percent, at least 10mole percent, at least 20 mole percent, or at least 50 mole percent ofthe carbonyl groups in the carbonyl-containing polymer precursor arereacted with the guanylating agent. Up to 100 mole percent, up to 90mole percent, up to 80 mole percent, or up to 60 mole percent of thecarbonyl groups can be reacted with the guanylating agent. For example,the guanylating agent can be used in amounts sufficient to functionalize0.1 to 100 mole percent, 0.5 to 100 mole percent, 1 to 90 mole percent,1 to 80 mole percent, 1 to 60 mole percent, 2 to 50 mole percent, 2 to25 mole percent, or 2 to 10 mole percent of the carbonyl groups in thecarbonyl-containing polymer.

The guanidinyl-containing polymer can be crosslinked. In someembodiments, the carbonyl-containing polymer is crosslinked prior toreaction with the guanylating agent. The carbonyl-containing polymer canbe crosslinked either by addition of a crosslinking monomer in themonomer composition used to form the carbonyl-containing polymer or byreaction of some of the carbonyl groups of the previously formedcarbonyl-containing polymer with a suitable crosslinking agent. In otherembodiments, crosslinking can occur after reaction of thecarbonyl-containing polymer with the guanylating agent. In thisembodiment, crosslinking can occur by reaction of some of the remainingcarbonyl groups (those carbonyl groups in the carbonyl-containingpolymer precursor that were not reacted in the process of forming theguanidinyl-containing polymer) with a suitable crosslinking agent or byreaction of some of the guanidinyl groups with a crosslinking agent.

Suitable crosslinking monomers for use in the monomer composition toform the carbonyl-containing polymer include, but are not limited to,N,N′-(hetero)alkylenebis(meth)acrylamide. These crosslinking monomershave at least two (meth)acryloyl groups that can react to crosslink onepolymeric chain with another polymeric chain or that can react tocrosslink one part of a polymeric chain with another part of the samepolymeric chain. Suitable N,N′-alkylenebis(meth)acrylamide crosslinkingmonomers include, but are not limited to, those having an alkylene groupwith 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms such asN,N′-methylenebisacrylamide, N,N′-methylenebismethacrylamide,N,N′-ethylenebisacrylamide, N,N′-ethylenebismethacrylamide,N,N′-propylenebisacrylamide, N,N′-propylenebismethacrylamide,N,N′-hexamethylenebisacrylamide, andN,N′-hexamethylenebismethacrylamide.SuitableN,N′-heteroalkylenebis(meth)acrylamide crosslinking monomersinclude, but are not limited to, N,N′-cystaminebisacrylamide,N,N′-piperazinebisacrylamide, and N,N′-piperazinebismethacrylamide.These crosslinking monomers are commercially available from varioussuppliers such as Sigma-Aldrich (Milwaukee, Wis.) and Polysciences, Inc.(Warrington, Pa.). Alternatively, these crosslinking monomers can besynthesized by procedures described in the art such as, for example, inRasmussen, et al., Reactive Polymers, 16, 199-212 (1991/1992).

Suitable crosslinkers for reaction with carbonyl groups of thecarbonyl-containing polymer precursor or remaining carbonyl groups ofthe guanidinyl-containing polymer include molecules comprising two ormore amine, hydrazine, hydrazide, or O-substituted hydroxylaminemoieties. Specific examples of polyamine (compounds with two or moreamine groups) crosslinkers include 1,2-ethanediamine,1,2-propanediamine, 1,3-propanediamine, 1,6-hexanediamine,tris-(2-aminoethyl)amine, diethylenetriamine, triethylenetetraamine,tetraethylenepentaamine, N,N′-bis(3-aminopropyl)piperazine,N-(2-aminoethyl)piperazine, polyethyleneimine, polyallylamine, and thelike. Specific examples of polyhydrazines (compounds with two or morehydrazine groups) include 1,1′-ethylenebishydrazine,1,1′-propylenebishydrazine, 1,1′-ethylenebis(1-cyclohexylhydrazine),1,1′-decamethylenebis(1-n-butylhydrazine), and the like. Specificexamples of useful polyhydrazides (compounds with two or more hydrazidegroups) include succinic dihydrazide, adipic dihydrazide, terephthalicdihydrazide, 1,3-diaminoguanidine, and the like. Specific examples ofpolyhydroxylamines (compounds with two or more O-substitutedhydroxylamine groups) include O,O′-ethylenebishydroxylamine(1,2-bisaminoxyethane), 1,6-bisaminoxyhexane, and the like.Alternatively, crosslinkers comprising two or more different moietiesselected from amine, hydrazine, hydrazide, or O-substitutedhydroxylamine moieties can be used.

Suitable crosslinkers for reaction with the guanidinyl groups of theguanidinyl-containing polymer include amine-reactive compounds such asbis- and polyaldehydes such as glutaraldehyde, bis- and polyepoxidessuch as butanedioldiglycidylether and ethyleneglycoldiglycidylether,polycarboxylic acids and their derivatives (e.g., acid chlorides),polyisocyanates, formaldehyde-based crosslinkers such as hydroxymethyland alkoxymethyl functional crosslinkers, such as those derived fromurea or melamine.

Rather than reacting a precursor polymer with a guanylating agent toprepare a guanidinyl-containing polymer, the guanidinyl-containingpolymer can be prepared by free radical polymerization of aguanidinyl-containing monomer, which refers to a monomer having anethylenically unsaturated group and a guanidinyl-containing group.Example guanidinyl-containing monomers are of Formula (IX) and (X).

In Formulas (IX) and (X), group R¹ is hydrogen, C₁-C₁₂ alkyl, or C₅-C₁₂(hetero)aryl. Group R² is a covalent bond, a C₂ to C₁₂ alkylene, aC₅-C₁₂ (hetero)arylene, a divalent group of formula

or a divalent group of formula

Group R¹⁰ is C₂ to C₁₂ alkylene, or C₅-C₁₂ (hetero)arylene. Each R³ isindependently hydrogen, hydroxyl, C₁-C₁₂ alkyl, or C₅-C₁₂ (hetero)aryl.R³ is preferably hydrogen or C₁-C₄ alkyl. Group R⁴ is hydrogen, C₁-C₁₂alkyl, C₅-C₁₂ (hetero)aryl, or —N(R³)₂. Preferably, R⁴ is hydrogen orC₁-C₄ alkyl. Group X is oxy or —NR³—. Group R⁶ is a C₂ to C₁₂ alkylene.Group R⁷ is hydrogen or CH₃.

The monomers of Formula (IX) and (X) can be formed, for example, by acondensation reaction of a carbonyl-containing monomer with theguanylating agent of Formula (VII). Example carbonyl-containing monomersinclude, but are not limited to, acrolein, vinyl methyl ketone, vinylethyl ketone, vinyl isobutyl ketone, isopropenyl methyl ketone, vinylphenyl ketone, diacetone (meth)acrylamide, acetonyl acrylate, andacetoacetoxyethyl (meth)acrylate.

The monomers of Formula (IX) or (X) may be reacted to form homopolymersor can be copolymerized with other ethylenically unsaturated monomerssuch as any of the hydrophilic monomers described above. A free radicalinitiator such as those described above in the preparation of thecarbonyl-containing polymer can be used. This reaction is furtherdescribed in International Patent Publication WO 2011/103106 A1(Rasmussen et al.).

Guanidinyl-containing polymers formed from a monomer of Formula (X) or(XI) are typically crosslinked by addition of a crosslinking monomer tothe monomer composition. Suitable crosslinking monomers includeN,N′-alkylenebis(meth)acrylamide,N,N′-heteroalkylenebis(meth)acrylamide, or a combination thereof. Morespecific crosslinkers are the same as described above for use in amonomer composition for preparation of the carbonyl-containing polymers.Alternatively, the guanidinyl-containing polymers can be formed withouta crosslinking monomer and the guanidinyl groups can be reacted withcrosslinkers as described above.

Wipes are provided that contain a substrate and a cationic coatingdisposed on a surface of the substrate, distributed throughout at leasta portion of the substrate, or both. The substrate is typically porousand includes a sponge, nonwoven fabric, or woven fabric. The cationiccoating includes the guanidinyl-containing polymer that is bound to thesubstrate. The guanidinyl-containing polymer can be bound to thesubstrate using any suitable method or means. In some embodiments, theguanidinyl-containing polymer is grafted (i.e., covalently attached) tothe substrate. In other embodiments, the guanidinyl-containing polymeris contacted with the substrate prior to crosslinking and is crosslinkedin the presence of the substrate. When the substrate includes fibers(e.g., the substrate includes a woven or nonwoven fabric), thecrosslinked guanidinyl-containing polymer can surround fibers. Thefibers and the crosslinked guanidinyl-containing polymers can be sointermingled that separation is not possible by a technique such aspeeling or dissolution or by any other technique without the destructionof the wipe.

The substrate may be in any suitable form for a wipe. Some suitablesubstrates are woven or non-woven fabrics that are in the form of asheet. The sheet can have any desired size and shape. Other suitablesubstrates are sponges that can have any desired size or shape. Thesubstrates are usually porous. Suitable substrates are typicallyflexible so that the wipe can easily conform and contact varioussurfaces such as those that are not flat.

The substrate may be formed from any suitable thermoplastic or thermosetmaterial. The material may be an organic polymeric material. Suitableorganic polymeric materials include, but are not limited to,poly(meth)acrylates, poly(meth)acrylamides, polyolefins,poly(isoprenes), poly(butadienes), fluorinated polymers, chlorinatedpolymers, polyamides, polyimides, polyethers, poly(ether sulfones),poly(sulfones), poly(vinyl acetates), copolymers of vinyl acetate, suchas poly(ethylene)-co-poly(vinyl alcohol), poly(phosphazenes), poly(vinylesters), poly(vinyl ethers), poly(vinyl alcohols), poly(carbonates),polyurethanes, and cellulosic materials.

Suitable polyolefins include, but are not limited to, poly(ethylene),poly(propylene), poly(1-butene), copolymers of ethylene and propylene,alpha olefin copolymers (such as copolymers of ethylene or propylenewith 1-butene, 1-hexene, 1-octene, and 1-decene),poly(ethylene-co-1-butene) and poly(ethylene-co-1-butene-co-1-hexene).

Suitable fluorinated polymers include, but are not limited to,poly(vinyl fluoride), poly(vinylidene fluoride), copolymers ofvinylidene fluoride (such as poly(vinylidenefluoride-co-hexafluoropropylene), and copolymers ofchlorotrifluoroethylene (such aspoly(ethylene-co-chlorotrifluoroethylene).

Suitable polyamides include, but are not limited to,poly(iminoadipoyliminohexamethylene),poly(iminoadipoyliminodecamethylene), and polycaprolactam. Suitablepolyimides include, but are not limited to, poly(pyromellitimide).

Suitable poly(ether sulfones) include, but are not limited to,poly(diphenylether sulfone) and poly(diphenylsulfone-co-diphenyleneoxide sulfone).

Suitable copolymers of vinyl acetate include, but are not limited to,poly(ethylene-co-vinyl acetate) and such copolymers in which at leastsome of the acetate groups have been hydrolyzed to afford variouspoly(vinyl alcohols).

Suitable cellulosic materials include cotton, rayon, and blends thereof.

In some embodiments, the substrate is formed from propylene polymers(e.g., homopolymer or copolymers). Polypropylene polymers, particularlypolypropylene homopolymers, can be desirable for some applications dueto properties such as non-toxicity, inertness, low cost, and the easewith which it can be extruded, molded, and formed into articles.Polypropylene polymers can be formed, for example, into porous sheets ofwoven or nonwoven fibers.

Some substrates are nonwoven fabrics. As used herein, the term “nonwovenfabric” refers to a fabric or web that has a structure of individualfibers or filaments that are randomly and/or unidirectionally interlaidin a mat-like fashion. The individual fibers or threads are notinterlaid in an identifiable pattern as in a knitted or woven fabric.Examples of suitable nonwoven fabrics include, but are not limited to,melt-blown fabrics, spun-bond fabrics, carded fabrics, wetlaid fabrics,and air-laid fabrics.

Spun-bonded fibers are typically small diameter fibers that are formedby extruding molten thermoplastic polymer as filaments from a pluralityof fine, usually circular capillaries of a spinneret with the diameterof the extruded fibers being rapidly reduced. Melt-blown fibers aretypically formed by extruding the molten thermoplastic material througha plurality of fine, usually circular, die capillaries as molten threadsor filaments into a high velocity, usually heated gas (e.g., air) streamwhich attenuates the filaments of molten thermoplastic material toreduce their diameter. Thereafter, the melt-blown fibers are carried bythe high velocity gas stream and are deposited on a collecting surfaceto from a fabric of randomly disbursed melt-blown fibers. Any of thenon-woven fabrics may be made from a single type of fiber or two or morefibers that differ in the type of thermoplastic polymer and/orthickness.

Wet-laid fibers can be formed into sheets by forming a slurry thatcontains a) fibers and b) a suspending liquid such as water, awater-miscible organic solvent, or a mixture thereof. The slurry isplaced in mold or deposited in a layer. The suspending liquid is removedto form a sheet or mat. The sheet or mat is then dried. In someembodiments, a polymeric binder is included in the dispersion. In otherembodiments, a polymeric binder can be applied after formation of asheet or mat. The polymeric binder is often a latex polymer.

Further details on the manufacturing method of nonwoven fabrics may befound in Wente, Superfine Thermoplastic Fibers, 48 INDUS. ENG. CHEM.1342(1956), or in Wente et al., Manufacture Of Superfine Organic Fibers,(Naval Research Laboratories Report No. 4364, 1954).

The cationic coating composition that includes the guanidinyl-containingpolymer is applied to the substrate. Coating methods include thetechniques commonly known such as dip, spray, knife, bar, slot, slide,die, roll, and gravure coating. The cationic coating can be disposed ona surface of the substrate or distributed throughout the substrate. Forexample, the cationic coating composition can be applied to the surfaceof the substrate. Depending on the porosity of the substrate, theviscosity of the cationic coating composition, and the relative volumeof the cationic coating composition to that of the substrate, at leastsome of the cationic coating composition can permeate into thesubstrate. In some examples, the cationic coating can be poured over thesubstrate such that the substrate is immersed in or covered with thecationic coating composition. The cationic coating composition oftenincludes a liquid such as water, an organic solvent such as a polarorganic solvent (e.g., a polar that is miscible with water), or amixture thereof. The cationic coating composition can additionallyinclude the crosslinking agent for the guanidinyl-containing polymer.Depending on the chemistry used to bind the gaunidinyl-containingpolymer to the substrate, a compound for grafting or attaching theguanidinyl-containing polymer to the substrate can be included in thecationic coating composition. After application to the substrate, thecationic coating composition can be dried to remove the liquid or anydesired portion of the liquid. In some embodiments, the drying to removethe liquid is accomplished through evaporation.

In some embodiments, the cationic coating composition is applied to thesubstrate by first applying the precursor polymer for theguanidinyl-containing polymer followed by application of the guanylatingagent. For example, an amino-containing polymer precursor or acarbonyl-containing polymer precursor can be applied to the substrate ina first coating composition. A second coating composition can then beapplied that includes the guanylating agent. The crosslinking agent canbe added in the first coating composition with the precursor polymer, inthe second coating composition with the guanylating agent, or in a thirdcoating composition. Any of the coating compositions can include anoptional compound for grafting the guanidinyl-containing polymer to thesubstrate.

In other embodiments, the guanidinyl-containing polymer is applied tothe substrate. The coating composition that contains theguanidinyl-containing polymer can further include a crosslinking agent,an optional grafting compound, or a mixture thereof. Alternatively, thecrosslinking agent and/or optional grafting agent can be added in asecond coating composition.

Some substrates have amine-reactive functional groups such as halidegroups, epoxy groups, ester groups, or isocyanate groups. Theseamine-reactive groups can react with amino groups of theguanidinyl-containing polymer. The amino groups can be part of theguanidinyl group (such as a terminal amino group) or any other aminogroups that are present in the guanidinyl-containing polymer. Forexample, if the guanidinyl-containing polymer was formed from anamino-containing polymer precursor, there can be amino groups in thebackbone of the guanidinyl-containing polymer.

The amine-reactive functional groups on the substrate may be part of thepolymeric material used to form the substrate or may be provided by anyof the techniques known to one in the art. In one embodiment, thesubstrate may have a primer layer containing a polymer havingamine-reactive functional groups. That is, the substrate includes a basepolymer layer and a primer layer. Especially useful polymers of use inthe primer layer are azlactone functional polymers such as thosedescribed in U.S. Pat. No. 7,101,621 (Haddad et al.). Such primer layercoatings are typically hydrophilic and are compatible with the cationiccoating composition. Useful coating techniques for the primer layerinclude applying a solution or dispersion of the polymer havingamine-reactive functional groups, optionally further including acrosslinker, onto the substrate. Coating methods include the techniquescommonly known such as dip, spray, knife, bar, slot, slide, die, roll,and gravure coating. The application step is generally followed byevaporating the solvent to form the polymer coating.

In some embodiments, the polymer having amine-reactive functional groupsmay be grafted to the surface of a substrate by ionizingradiation-initiated graft polymerization of a monomer having afree-radically polymerizable group and a second functional groupreactive with the guanidinyl-containing polymer. One such polymer havingan amine-reactive functional group is described U.S. Patent ApplicationPublication No. 2010/0075560 (Seshadri et al.). Suitable monomersinclude, for example, an azlactone-functional monomer, isocyanatoethyl(meth)acrylate, and a glycidyl (meth)acrylate. Other suitable monomersinclude, for example, those having a carbonyl group as described in U.S.Pat. No. 8,377,672 (Rasmussen et al.). The monomers can graft (i.e.,form a covalent bond) to the surface of the substrate when exposed to anionizing radiation, preferably e-beam or gamma radiation. That is,reaction of an ethylenically unsaturated group (e.g., a (meth)acryloylgroup) of the monomer with the surface of the substrate in the presenceof the ionizing radiation results in grafting to the substrate via theethylenically unsaturated group.

Some substrates have carbonyl-reactive groups such as amines. Thesecarbonyl-reactive groups can react with a carbonyl-containing polymerprecursor prior to reaction with the guanylating agent or can react withany residual carbonyl groups in the guanidinyl-containing polymer afterreaction with the guanylating agent.

The carbonyl-reactive functional groups on the substrate may be part ofthe polymeric material used to form the substrate or may be provided byany of the techniques known to one in the art. In some embodiments, thecarbonyl-reactive groups can be grafted to the surface of a substrate byionizing radiation-initiated graft polymerization of a monomer having afree-radically polymerizable group and a second group capable ofreacting with a carbonyl group of either the carbonyl-containingprecursor or any residual carbonyl groups in the guanidinyl-containingpolymer after reaction with a guanylating agent. Such monomers arevarious amino-containing monomers such as those of Formula (V) where R⁸is hydrogen.

In another method of bonding the guanidinyl-containing polymer to thesubstrate, a compound such as benzophenone or acetophenone can be addedto the monomer composition used to form the carbonyl-containingprecursor. Upon exposure to UV radiation, the benzophenone oracetophenone can abstract a hydrogen atom from the polymeric material ofthe substrate. This abstraction results in the formation of a freeradical site on the polymeric material of the substrate. The monomersthen interact with the free radical site and become graft polymerizedonto the substrate. The covalently attached carbonyl-containing polymercan then be treated with a guanylating agent to form theguanidinyl-containing polymer.

The bonding of the guanidinyl-containing polymer to the substrateprovides enhanced affinity for various microorganisms while retainingmany of the desirable features of the substrate such as mechanicalstability, thermal stability, porosity, and flexibility. The wipestypically contain an amount of the bound guanidinyl-containing polymerin a range of 0.1 to 10 weight percent, in a range of 0.1 weight percentto 50 weight percent, in a range of 0.1 to 3 weight percent, in a rangeof 0.1 to 2, or in a range of 0.1 weight percent to 1 weight percent,based on a total weight of the wipe.

A method of removing microorganisms from a microorganism-contaminatedsurface is provided. The method includes preparing a wipe that includes(a) a substrate comprising a sponge, a woven fabric, or nonwoven fabricand (b) a cationic coating disposed on a surface of the substrate,distributed throughout at least a portion of the substrate, or both. Thecationic coating includes a guanidinyl-containing polymer that iscrosslinked, that is covalently attached to the substrate, or both. Themethod further includes contacting the wipe in the presence of a liquidwith an area of the microorganism-contaminated surface, wherein at least99 percent of microorganisms present in the area are removed from themicroorganism-contaminated surface.

The wipes are suitable for the removal of microorganisms, especiallyspores, from a microorganism-contaminated surface. Bacterial spores areknown to be adherent and difficult to remove from a variety of surfaces,as well as being resistant to most antimicrobial treatments. Because theguanidinyl-containing polymer can interact with microorganisms, the wipecan remove the microorganisms from a surface and prevent their transferto another surface. The removal of the microorganisms is believed to be,at least in part, due to an ionic interaction. The guanidinyl group ofthe guanidinyl-containing polymer is typically positively charged overnearly the entire pH range available in aqueous media, and will bindnegatively charged or near neutral species. All cells, includingmicroorganisms, are negatively charged due to the presence of groups,such as carboxylates, sulfates, or phosphates, on their surfaces.Positively charged species are likely not to bind.

The wipe can be used for the removal of various microorganismsincluding, for example, bacteria (gram-positive bacteria andgram-negative bacteria), fungi, yeasts, protozoans, viruses (envelopedviruses and non-enveloped viruses (norovirus, poliovirus, hepatitis Avirus, rhinovirus, and combinations thereof)), bacterial spores (forexample, endospore forms of Bacillus and Clostridium microorganisms),and the like, and combinations thereof.

Genera of microorganisms to be removed include, but are not limited to,Listeria, Escherichia, Salmonella, Campylobacter, Clostridium,Helicobacter, Mycobacterium, Staphylococcus, Shigella, Enterococcus,Bacillus, Neisseria, Shigella, Streptococcus, Vibrio, Yersinia,Bordetella, Borrelia, Pseudomonas, Saccharomyces, Candida, and the like,and combinations thereof.

Specific microorganism strains that can be targets for detection includeEscherichia coli, Yersinia enterocolitica, Yersinia pseudotuberculosis,Vibrio cholerae, Vibrio parahaemolyticus, Vibrio vulnificus, Listeriamonocytogenes, Staphylococcus aureus, Salmonella enterica, Saccharomycescerevisiae, Candida albicans, Staphylococcal enterotoxin ssp, Bacilluscereus, Bacillus anthracis, Bacillus atrophaeus, Bacillus subtilis,Clostridium perfringens, Clostridium botulinum, Clostridium difficile,Clostridium sporogenes, Enterobacter sakazakii, Pseudomonas aeruginosa,and the like, and combinations thereof.

Microorganisms (including spore forms) that have been captured or bound(for example, by adsorption) by the wipe can be detected by essentiallyany desired method that is currently known or hereafter developed. Suchmethods include, for example, culture-based methods (which can bepreferred when time permits), microscopy (for example, using atransmitted light microscope or an epifluorescence microscope, which canbe used for visualizing microorganisms tagged with fluorescent dyes) andother imaging methods, immunological detection methods, and geneticdetection methods. The detection process following microorganism captureoptionally can include washing to remove sample matrix components.

Suitable culture-based methods of detecting microorganisms can includethe use of a thin film culture plate device (e.g., an Aerobic CountPETRIFILM culture plate device, commercially available from 3M Co., St.Paul, Minn., or the thin film culture plate devices described in U.S.Pat. No. 4,565,783 (Hansen et al.), U.S. Pat. No. 5,089,413 (Hansen etal.), and U.S. Pat. No. 5,232,838 (Crandall et al.)).

Immunological detection is detection of an antigenic material derivedfrom a target organism, which is commonly a biological molecule (forexample, a protein or proteoglycan) acting as a marker on the surface ofbacteria or viral particles. Detection of the antigenic materialtypically can be by an antibody, a polypeptide selected from a processsuch as phage display, or an aptamer from a screening process.

Immunological detection methods are well-known and include, for example,immunoprecipitation and enzyme-linked immunosorbent assay (ELISA).Antibody binding can be detected in a variety of ways (for example, bylabeling either a primary or a secondary antibody with a fluorescentdye, with a quantum dot, or with an enzyme that can producechemiluminescence or a colored substrate, and using either a platereader or a lateral flow device).

Detection can also be carried out by genetic assay (for example, bynucleic acid hybridization or primer directed amplification), which isoften a preferred method. The captured or bound microorganisms can belysed to render their genetic material available for assay. Lysismethods are well-known and include, for example, treatments such assonication, osmotic shock, high temperature treatment (for example, fromabout 50° C. to about 100° C.), and incubation with an enzyme such aslysozyme, glucolase, zymolose, lyticase, proteinase K, proteinase E, andviral enolysins.

Many commonly-used genetic detection assays detect the nucleic acids ofa specific microorganism, including the DNA and/or RNA. The stringencyof conditions used in a genetic detection method correlates with thelevel of variation in nucleic acid sequence that is detected. Highlystringent conditions of salt concentration and temperature can limit thedetection to the exact nucleic acid sequence of the target. Thusmicroorganism strains with small variations in a target nucleic acidsequence can be distinguished using a highly stringent genetic assay.Genetic detection can be based on nucleic acid hybridization where asingle-stranded nucleic acid probe is hybridized to the denaturednucleic acids of the microorganism such that a double-stranded nucleicacid is produced, including the probe strand. One skilled in the artwill be familiar with probe labels, such as radioactive, fluorescent,and chemiluminescent labels, for detecting the hybrid following gelelectrophoresis, capillary electrophoresis, or other separation method.

Particularly useful genetic detection methods are based on primerdirected nucleic acid amplification. Primer directed nucleic acidamplification methods include, for example, thermal cycling methods (forexample, polymerase chain reaction (PCR), reverse transcriptasepolymerase chain reaction (RT-PCR), and ligase chain reaction (LCR)), aswell as isothermal methods and strand displacement amplification (SDA)(and combinations thereof; preferably, PCR or RT-PCR). Methods fordetection of the amplified product are not limited and include, forexample, gel electrophoresis separation and ethidium bromide staining,as well as detection of an incorporated fluorescent label or radio labelin the product. Methods that do not require a separation step prior todetection of the amplified product can also be used (for example,real-time PCR or homogeneous detection).

Bioluminescence detection methods are well-known and include, forexample, adensosine triphosphate (ATP) detection methods including thosedescribed in U.S. Pat. No. 7,422,868 (Fan et al.).

When the wipe is contacted in the presence of a liquid with an area of amicroorganism-contaminated surface, at least 99 percent of themicroorganisms are removed from the area contacted with the wipe. Insome embodiments, at least 99.1 percent, at least 99.2 percent, at least99.3 percent, at least 99.4 percent, at least 99.5 percent, at least99.6 percent, at least 99.7 percent, at least 99.8 percent, or even atleast 99.9 percent of the microorganisms are removed from the areacontacted with the wipe.

Liquid is typically present in the area of themicroorganism-contaminated surface that is contacted with the wipe. Theliquid can be present on the wipe, on the microorganism-contaminatedsurface, or both. The liquid is typically water, a water-miscibleorganic solvent, or a mixture thereof. Suitable water-miscible organicsolvents are often alcohols such as those having 1 to 4 carbon atoms(e.g., methanol, ethanol, isopropanol). In many embodiments, the liquidis water or a mixture of water and the water-miscible organic solvent.The liquid typically contains at least 10 weight percent, at least 20weight percent, or at least 50 weight percent water based on a totalweight of the liquid. The amount of water can be up to 100 weightpercent, up to 90 weight percent, up to 80 weight percent, or up to 60weight percent of the liquid.

The liquid can include other ingredients suitable for removal ofmicroorganisms from a microorganism-contaminated surface such as, forexample, a disinfectant or other suitable cleaning aids, including thosecommonly used on hard surfaces. These other ingredients are typicallysoluble in water and/or a water-miscible organic solvent. Examples ofsuitable disinfectants can include, but are not limited to, loweralcohols, oxidizing agents (e.g., hydrogen peroxide, peracetic acid,sodium hypochlorite, and the like), phenolics, quaternary ammoniumcompounds, antimicrobial biguanides, and antimicrobial metals.

In some embodiments, the wipe is provided in a wet form. That is thewipe includes a liquid. The amount of liquid can be up to 10 times, 9times, 8 times, 7 times, 6 times, 5 times, 4.5 times, 4 times, 3.5times, 3 times, 2 times or even up to 1 times of the weight of the drywipe, (i.e., the weight of the wipe without the liquid, whichcorresponds to the weight of the substrate plus the weight of thecationic coating). In some embodiments, the wet wipe is at least 0.1times, 0.2 times, 0.3 times. 0.4 times, or even at least 0.5 times ofthe weight of the dry wipe.

The wipes are useful, for example, for removing microorganisms from amicroorganism-contaminated surface, or for wiping surfaces suspected ofbeing contaminated. For example, the wipes are useful for wipingsurfaces (e.g., solid surfaces) in a hospital room, surfaces in a foodpreparation or serving area, and surfaces frequently touched such asdoor knobs, handrails, and the like.

The binding of microorganisms to the coated wipes is preferablyessentially irreversible in order to minimize transfer of themicroorganisms to another surface or to the same surface after cleaning.In some embodiments, when the wipe is brought in contact with a secondsurface or brought in contact with the previously cleaned surface afterbeing in contact with a microorganism-contaminated surface, the wipetransfers no more than 0.2 percent, no more than 0.1 percent, no morethan 0.09 percent, no more than 0.08 percent, no more than 0.07 percent,no more than 0.06 percent, no more than 0.05 percent, no more than 0.04percent, no more than 0.03 percent, no more than 0.02 percent, or evenno more than 0.01 percent, of the number of microorganisms removed froma microorganism-contaminated surface to the other surface.

The high removal of microorganisms from a microorganism-contaminatedsurface and the low transfer of microorganisms to another surface or tothe same surface after cleaning is believed to be a uniquecharacteristic of the guanidinyl group of the guanidinyl-containingpolymer coating. In addition to the ionic interaction between thepositively charged guanidinyl group and the negatively chargedmicroorganisms, the guanidinyl group is capable of additional types ofinteraction, including hydrogen bonding and hydrophobic interactiontypes of binding. These additional types of interaction may increase thestrength of the binding interaction between the coated wipe and themicroorganism and, in some instances, make it essentially irreversible.This binding interaction is often maintained under a variety ofconditions, such as over wide pH ranges, under high ionic strengthconditions, and in the presence of other additives, such as surfactants.

The low transfer is also facilitated by the crosslinking of theguanidinyl-containing polymer and/or the binding of the cationic coating(e.g., binding of the guanidinyl-containing polymer) to the substrate.The crosslinked or grafted guanidinyl-containing polymer is typicallynot soluble in the liquid used with the wipe which results in minimalresidue being left behind on a surface after being cleaned with thewipe. The binding of the cationic coating to the substrate furtherincreases the likelihood that the removed microorganisms will not betransferred to another surface but will remain on the wipe.

In many embodiments, the wipes are disposable after use.

The present invention is described above and further illustrated belowby way of examples, which are not to be construed in any way as imposinglimitations upon the scope of the invention. On the contrary, it is tobe clearly understood that resort may be had to various otherembodiments, modifications, and equivalents thereof which, after readingthe description herein, may suggest themselves to those skilled in theart without departing from the spirit of the present invention and/orthe scope of the appended claims.

Various embodiments are provided that include a wipe and a method ofusing the wipe to remove microorganisms.

Embodiment 1 is a wipe that includes (a) a substrate comprising asponge, a woven fabric, or nonwoven fabric and (b) a cationic coatingdisposed on a surface of the substrate, distributed throughout at leasta portion of the substrate, or both. The cationic coating contains aguanidinyl-containing polymer that is crosslinked, covalently bonded tothe substrate, or both. When the wipe is contacted in the presence of aliquid with an area of a microorganism-contaminated surface, at least 99percent of microorganisms present on the microorganism-contaminatedsurface are removed from the area by the wipe, and when the wipe iscontacted in the presence of the liquid with the area of themicroorganism-contaminated surface and then contacted with a secondsurface, no more than 0.2 percent of the microorganisms are transferredfrom the wipe to the second surface.

Embodiment 2 is the wipe of embodiment 1, wherein theguanidinyl-containing polymer is a reaction product of (a) a guanylatingagent and (b) a carbonyl-containing polymer precursor or anamino-containing polymer precursor.

Embodiment 3 is the wipe of one of embodiment 1 or 2, wherein theguanidinyl-containing polymer is of the Formula (I):

wherein R¹ is hydrogen, C₁-C₁₂ (hetero)alkyl, a C₅-C₁₂ (hetero)aryl, ora residue of the polymer chain; R² is a covalent bond, a C₂ to C₁₂(hetero)alkylene, or a C₅-C₁₂ (hetero)arylene; R³ is hydrogen, C₁-C₁₂(hetero)alkyl, C₅-C₁₂ (hetero)aryl, or a residue of the polymer chainwhen n is 0; each R⁴ is independently hydrogen, C₁-C₁₂ (hetero)alkyl,C₅-C₁₂ (hetero)aryl; R⁵ is hydrogen, C₁-C₁₂ (hetero)alkyl, or C₅-C₁₂(hetero)aryl, or —N(R⁴)₂; n is 0 or 1; m is 1 or 2; and x is an integerequal to at least 1.

Embodiment 4 is the wipe of embodiment 3, wherein theguanidinyl-containing polymer is of Formula (II).

Embodiment 5 is the wipe of embodiment 3, wherein theguanidinyl-containing polymer is of Formula (IV).

Embodiment 6 is the wipe of any one of embodiments 1 to 3 or 5, whereinthe guanidinyl-containing polymer is a reaction product of (a) aguanylating agent and (b) a carbonyl-containing polymer precursor, andwherein 1 to 90 mole percent of the carbonyl groups of thecarbonyl-containing polymer precursor are reacted with the guanylatingagent.

Embodiment 7 is the wipe of any one of embodiments 1 to 3 or 5, whereinthe guanidinyl-containing polymer is a reaction product of (a) aguanylating agent and (b) a carbonyl-containing polymer precursor, andwherein the guanidinyl-containing polymer is crosslinked with aN,N′-(hetero)alkylenebis(meth)acrylamide.

Embodiment 8 is the wipe of any one of embodiments 1 to 4, wherein theguindidinyl-containing polymer is a reaction product of a (a)guanylating agent and (b) an amino-containing polymer precursor, andwherein 1 to 90 mole percent of the amino groups of the amino-containingpolymer precursor are reacted with the guanylating agent.

Embodiment 9 is the wipe of any one of embodiments 1 to 4 wherein theguanidinyl-containing polymer is a reaction product of (a) a guanylatingagent and (b) an amino-containing polymer, and wherein theguanidinyl-containing polymer is crosslinked with a polyglycidylether.

Embodiment 10 is the wipe of any one of embodiments 1 to 9, wherein theguanidinyl-containing polymer is present in an amount of 0.1 weightpercent to 10 weight percent based on a total weight of the wipe.

Embodiment 11 is the wipe according to any one of embodiments 1 to 10,wherein the liquid comprises water, a water-miscible organic solvent, ora mixture thereof.

Embodiment 12 is the wipe according to any one of embodiments 1 to 11,wherein the substrate is a woven fabric or nonwoven fabric comprisingfibers and wherein the crosslinked guanidinyl-containing polymersurrounds at least some of the fibers.

Embodiment 13 is the wipe according to any one of embodiments 1 to 12,wherein the guanidinyl-containing polymer is covalently attacheddirectly to the substrate.

Embodiment 14 is the wipe according to any one of embodiments 1 to 13,wherein the substrate further comprises a base polymer layer and aprimer layer and wherein the cationic coating is covalently attached tothe primer layer.

Embodiment 15 is a method of removing microorganisms from amicroorganism-contaminated surface. The method includes preparing a wipethat includes (a) a substrate comprising a sponge, a woven fabric, ornonwoven fabric and (b) a cationic coating disposed on a surface of thesubstrate, distributed throughout at least a portion of the substrate,or both. The cationic coating contains a guanidinyl-containing polymerthat is crosslinked and that is bound to the substrate. The methodfurther includes contacting the wipe in the presence of a liquid with anarea of the microorganism-contaminated surface, wherein at least 99percent of microorganisms present on the microorganism-contaminatedsurface are removed from the area by the wipe.

Embodiment 16 is the method of embodiment 15, wherein theguanidinyl-containing polymer is a reaction product of (a) a guanylatingagent and (b) a carbonyl-containing polymer precursor or anamino-containing polymer precursor.

Embodiment 17 is the method of embodiment 15 or 16, wherein theguanidinyl-containing polymer is of the Formula (I):

wherein R¹ is hydrogen, C₁-C₁₂ (hetero)alkyl, a C₅-C₁₂ (hetero)aryl, ora residue of the polymer chain; R² is a covalent bond, a C₂ to C₁₂(hetero)alkylene, or a C₅-C₁₂ (hetero)arylene; R³ is hydrogen, C₁-C₁₂(hetero)alkyl, C₅-C₁₂ (hetero)aryl, or a residue of the polymer chainwhen n is 0; each R⁴ is independently hydrogen, C₁-C₁₂ (hetero)alkyl,C₅-C₁₂ (hetero)aryl; R⁵ is hydrogen, C₁-C₁₂ (hetero)alkyl, or C₅-C₁₂(hetero)aryl, or —N(R⁴)₂; n is 0 or 1; m is 1 or 2; and x is an integerequal to at least 1.

EXAMPLES

Materials used in the preparation of examples of coated wipes are listedin Table 1:

TABLE 1 Material Description Aminoguanidine sulfate aminoguanidinesulfate, obtained from Alfa Aesar, Ward Hill, PA BenzophenoneBenzophenone, Sigma-Aldrich Co., Milwaukee, WI Benzyl bromide Benzylbromide, obtained from Sigma-Aldrich Co BUDGE Butanedioldiglycidylether,obtained from TCI America, Portland, OR t-Butanol t-Butanol, obtainedfrom Sigma-Aldrich Co. Cellulose cloth A cellulose based nonwoven clothhaving a basis weight of 48.5 grams/meter², obtained from SuominenCorporation, Windsor Locks, CT, product code WL 102010 Concentrated HClConcentrated hydrochloric acid, obtained from EMD Chemicals,Philadelphia, PA Diacetoneacrylamide Diacetoneacrylamide, obtained fromAlfa Aesar, Ward Hill, PA DicyclohexylcarbodiimideDicyclohexylcarbodiimide, obtained from Alfa Aesar, Ward Hill, PA IPA2-propanol, obtained from EMD Chemicals, Philadelphia, PAMethylenebisacrylamide Methylenebisacrylamide, obtained fromSigma-Aldrich Co. O-Methylisourea O-Methylisourea hemisulfate, obtainedfrom hemisulfate Alfa Aesar. PEI Polyethylenimine, Catalog #00618,70,000 MW, 30% w/w solution in water, obtained from Polysciences,Warrington, PA SCOTCH-BRITE cloth An absorbent nonwoven counter cloth,obtained from 3M Co., St. Paul, MN, under the trade designation“SCOTCH-BRITE ABSORBENT COUNTER CLOTH” SONTARA 8005 Apolyethyleneterephthalate (“PET”) nonwoven wipe, obtained from DuPontCo., Wilmington, DE, under the trade designation “SONTARA 8005”

Comparative Examples 1 to 4 (C1 to C4)

For each of Comparative Examples 1 to 4, a sample of Sontara 8005 PETnonwoven material (ca. 20 cm by 25 cm) was used, without addition of acoating material of the present disclosure.

Comparative Example 5 (C5): PEI Coated Nonwoven Wipe

Comparative Example 5 includes a PET nonwoven material coated with apolyethyleneimine polymer but without guanidinyl functionalization. Asample of polyethyleneimine, 70,000 MW (16.7 grams of a 30% by weightsolution in water) was diluted to a total of 500 grams with deionizedwater. BUDGE (2.35 grams) was diluted to a total of 500 grams withdeionized water, mixed thoroughly, then added to the PEI solution, andthe mixture mixed thoroughly. This coating solution was poured into arectangular glass dish and used to coat sheets of nonwoven material(SONTARA 8005) by a procedure similar to that described in Example 1(see below). The coated sheets were dried, then washed and dried asdescribed in Example 1 (see below).

Comparative Example 6 (C6)

Comparative Example 6 was a sample of cellulose sponge material(obtained from 3M Co., St. Paul, Minn., under the trade designation“SCOTCH-BRITE ABSORBENT COUNTER CLOTH”), without addition of a coatingmaterial of the present disclosure.

Comparative Example 7 (C7)

Comparative Example 7 was a sample of cellulose nonwoven cloth, withoutaddition of a coating material of the present disclosure.

Example 1 (Ex. 1): 25% Guanylated Polyethyleneimine (“G-PEI”) CoatedNonwoven Wipe

Polyethylenimine, 70,000 MW (658.2 grams of a 30 wt. % solution inwater, 4.59 amine equivalents) was charged to a 3 L 3-necked roundbottom flask equipped with overhead stirring. O-methylisoureahemisulfate (141.2 grams, 1.15 equivalents) was charged to a 1 L beaker,and enough deionized water was added to bring the total weight to 652.8grams. The contents of the beaker were stirred magnetically until all ofthe O-methylisourea hemisulfate dissolved, then the solution was pouredinto the round bottom flask. The reaction mixture was allowed to stir atambient temperature overnight (about 22 hours). Analysis by NMRspectroscopy indicated conversion to the desired product. Percent solidswas determined using an Ohaus moisture balance (Model Number MB35,obtained from Ohaus Corp., Parsippany, N.J.), and found to be 25.3 wt.%.

A sample of the G-PEI solution prepared as above (19.79 grams of a 25.3wt. % solids solution) was diluted to a total of 1000 grams withdeionized water. BUDGE (2.35 grams) was added and the mixture was mixedthoroughly. The solution was poured into a rectangular glass dish.Sheets of a PET nonwoven material, SONTARA 8005 (ca. 20 cm by 25 cm),were placed into the dish and submerged in the coating bath using aplastic beaker until they appeared to be thoroughly wetted withsolution. The G-PEI coated nonwoven material was placed between twosheets of polyester film and a 2.28 kilogram roller was rolled over themto remove excess coating solution. The G-PEI coated nonwoven sheets werethen removed from the liners and placed in trays to air dry. The G-PEIcoated nonwoven sheets were individually placed into 1 gallonpolyethylene jars, rinsed with deionized water, then allowed to soak indeionized water overnight. The wash water was poured off, the G-PEIcoated nonwoven sheets were rinsed with deionized water again, andplaced on trays to air dry. When small pieces of the G-PEI coatednonwoven sheets were placed into an aqueous solution of fluoresceindisodium salt (0.01 wt. %), they were stained a deep orange-red color.In contrast, nonwovens sheets lacking the G-PEI coating gave no colorchange when treated with the fluorescein disodium salt.

Example 2 (Ex. 2): Poly(Diacetoneacrylamide Guanylhydrazone) (“DA”)Grafted Nonwoven Wipe

Diacetoneacrylamide (50 grams), methylenebisacrylamide (1 gram), andbenzophenone (2.5 grams) were dissolved in methanol and diluted to atotal solution weight of 500 grams. The solution was poured into arectangular glass dish. Sheets of nonwoven material, SONTARA 8005 (ca.20 cm by 25 cm), were pre-wet with ethanol, then soaked in the monomersolution for 1 minute, sandwiched between two sheets of polyester filmand a 2.28 kilogram roller was rolled over them to remove excess coatingsolution. Ultraviolet (“UV”) grafting was conducted using a UV stand(obtained from Classic Manufacturing, Inc., Oakdale, Minn., equippedwith 18 bulbs (SYLVANIA RG2 40W F40/350BL/ECO bulbs, 10 bulbs above and8 bulbs 3.5 cm below the substrate, 117 cm long, spaced 5.1 cm oncenter), with an irradiation time of 15 minutes. After grafting, thegrafted nonwoven sheets were washed for 45 minutes each with 0.9%saline, 0.9% saline, and deionized water. The DA grafted nonwoven sheetswere then placed into a polyethylene bottle containing aminoguanidinesulfate (246 grams) and concentrated hydrochloric acid (5 mL) in 2liters of deionized water, and allowed to mix on a roller over theweekend. The DA grafted nonwoven sheets were washed again as describedabove and allowed to dry. When small pieces of the DA grafted nonwovensheets were placed into an aqueous solution of fluorescein disodium salt(0.01% w/w), they were stained a deep orange-red color.

Example 3 (Ex. 3): 25% Guanylated, 10% Benzylated PEI (“BG-PEI”) CoatedNonwoven Wipe

A 25% G-PEI solution prepared as above (300 grams of solution, 25.3 wt.% in water; the weight percentage was relative to amine equivalentweight) was charged to a 1 L round bottom flask. Benzyl bromide (19.74grams) was dissolved in methanol to provide a total of 300 grams ofsolution, and this solution was then added to the round bottom flask.The flask was attached to a rotating mixer and immersed in a water bathmaintained at 30° C. for 5 hours. Analysis by NMR indicated completeconversion to the desired product. A total of 339 grams of solvent wasthen stripped from the reaction mixture under vacuum, and 121 grams ofdeionized water was added to the resultant mixture. Percent solids wasdetermined using an Ohaus moisture balance, and found to be 23.7 wt. %solids.

A sample of the BG-PEI solution prepared as above (21.1 grams of a 23.7wt. % solids solution) was diluted to a total of 500 grams withdeionized water. BUDGE (2.35 grams) was added to 500 g of deionizedwater and the mixture was mixed thoroughly. The two solutions werecombined, mixed thoroughly, and poured into a rectangular glass dish.Sheets of a PET nonwoven material, SONTARA 8005 (ca. 20 cm by 25 cm),were placed into the dish and submerged in the coating bath using aplastic beaker until they appeared to be thoroughly wetted withsolution. The BG-PEI coated nonwoven material was placed between twosheets of polyester film and a 2.28 kilogram roller was rolled over themto remove excess coating solution. The BG-PEI coated nonwoven sheetswere then removed from the liners and placed in trays to air dry. TheBG-PEI coated nonwoven sheets were individually placed into 1 gallonpolyethylene jars, rinsed with deionized water, then allowed to soak indeionized water overnight. The wash water was poured off, and the BG-PEIcoated nonwoven sheets were rinsed with deionized water again, andplaced on trays to air dry. When small pieces of the BG-PEI coatednonwoven sheets were placed into an aqueous solution of fluoresceindisodium salt (0.01% w/w), they were stained a deep orange-red color. Incontrast, nonwovens sheets lacking the coating gave no color change whentreated with the fluorescein disodium salt.

Example 4 (Ex. 4): 25% p-chlorophenylbiguanidinyl PEI (25% CPB-PEI)Coated Nonwoven Wipe

Preparation ofN—[N-(4-chlorophenyl)carbamimidoyl]pyrazole-1-carboxamidinehydrochloride. A 1-L round bottom flask was charged with1-(4-chlorophenyl)-3-cyano-guanidine (24.2 g, 125 mmol, preparedaccording to the procedure in Hill et al., J Org. Chem., 1984, 49,1819-1823) and 250 mL of dioxane. The mixture was heated to about 50° C.and then treated with pyrazole (8.50 g, 125 mmol) and 31.3 mL of 4N HClin dioxane (125 mmol). The flask was equipped with a condenser and thereaction temperature was increased to 120° C. At this point all of thestarting material had dissolved. The temperature was maintained at 120°C. and a solid white mass formed soon after. Heating was continued for 1h and then the reaction was cooled. The white solid was broken up with aspatula and then isolated by filtration. The material was washed withTHF and then transferred to a round bottom flask. The material was thendried under reduced pressure to giveN—[N-(4-chlorophenyl)carbamimidoyl]pyrazole-1-carboxamidinehydrochloride (33.1 g) as a white powder.

Polyethylenimine, 70,000 MW (10.0 grams of a 30% w/w solution in water,156 mmol amine equivalents) was charged to a 250 mL round bottom flaskequipped with a magnetic stirbar. Deionized water (100 mL) was addedfollowed by theN—[N-(4-chlorophenyl)carbamimidoyl]pyrazole-1-carboxamidinehydrochloride (5.21 g, 17.4 mmol) prepared as above. The reactionmixture was heated to 100° C. and stirred under nitrogen overnight. Themilky reaction mixture was then cooled, diluted to 300 mL with deionizedwater and transferred to a 1 liter polyethylene jar. A 46 cm by 122 cmsheet of SONTARA 8005 PET nonwoven material was then placed in the jar.A solution of BUDGE (1.41 g, 6.98 mmol), diluted to 300 mL withdeionized water was then added and the polyethylene bottle was shakenvigorously for 2 minutes to thoroughly coat the nonwoven sheet. Thecoated nonwoven sheet was removed and carefully squeezed to removeexcess coating solution. The coated nonwoven sheet was then folded inthe opposite direction and returned to the polyethylene jar and shakenfor an additional 2 min. Again, the coated nonwoven sheet was removedand carefully squeezed to remove excess coating solution. After beingallowed to air dry overnight, the CPB-PEI coated nonwoven sheet wasplaced in a 1-L polyethylene jar and washed with 1 L of deionized water,with vigorous shaking, for 30 min. The water was removed and the washingprocedure was repeated. The CPB-PEI coated nonwoven sheet was thencarefully squeezed dry and allowed to air dry.

Example 5 (Ex. 5): 25% N,N′-dicyclohexyl Guanylated PEI (“DCHG-PEI”)Coated Nonwoven

Polyethylenimine, 70,000 MW (22.2 grams of a 30 wt. % solution in water,156 mmol amine equivalents) was charged to a 250 mL round bottom flaskequipped with a magnetic stirbar. Dicyclohexylcarbodiimide (8.0 grams,39 mmol) was added followed by 80 mL of t-butanol. The reaction washeated to 80° C. and stirred under nitrogen overnight. The reactionmixture was then cooled and concentrated under reduced pressure. Theresulting syrup was concentrated from ethanol several times to giveproduct as a milky syrup. Analysis by NMR spectroscopy indicatedessentially complete conversion to the desired product. The polymer wasthen diluted with IPA (159 mL) to give a solution calculated to be 8.5%solids.

DCHG-PEI (5.0 g, calculated to be 5.6 mmol of amine equivalents) wasdiluted to 25 g with IPA in an 8 oz jar. A solution of BUDGE (118 mg),diluted to 25 g in IPA was then added and the mixture was mixedthoroughly. Three 20 cm by 20 cm sheets of SONTARA 8005 PET nonwovenmaterial were then placed in the jar and the jar was capped with aTeflon-lined screw cap. The jar was shaken vigorously for two minutes.The DCHG-PEI coated nonwoven sheets were removed and carefully squeezedto remove excess coating solution. After being allowed to air dryovernight, the DCHG-PEI coated nonwoven sheets were placed into a 32 oz.polyethylene jar and washed in IPA, with vigorous shaking, for 15 min.The washing procedure was repeated with 1:1 IPA/deionized water and afinal wash with deionized water. The DCHG-PEI coated nonwoven sheetswere then allowed to air dry overnight.

Example 6 (Ex. 6): G-PEI Coated Nonwoven Wipe

Example 6 was a repeat run of making a G-PEI coated wipe, according tothe details in Example 1.

Example 7 (Ex. 7): 25% Guanylated G-PEI Coated Sponge Cloth

Sheets of sponge cloth (17 cm×20 cm, SCOTCH-BRITE Absorbent CounterCloths, available from 3M Co., St. Paul, Minn.) were individually placedinto 2000 mL polyethylene bottles filled with deionized water. Thebottles were sealed and placed on a shaker for 1 hour. The water waspoured off. This washing procedure was repeated five more times, thenthe washed sponge cloths were allowed to air dry.

A coating solution was prepared as described in Example 1 from G-PEI,BUDGE, and deionized water. The washed and dried sponge cloths werecoated and washed as described in Example 1.

Example 8 (Ex. 8): 25% Guanylated G-PEI Coated Cellulose Cloth

Sheets of a cellulose based nonwoven material having a basis weight of48.5 grams/meter² (available from Suominen Corporation, Windsor Locks,CT, product code WL 102010) were coated according to the procedure usedin Example 1, to obtain a G-PEI coated cellulose cloth.

Test Method for Removal of Microorganisms from aMicroorganism-Contaminated Surface and Transfer Contamination

Materials used in the “Test Method for Removal of Microorganisms from aMicroorganism-contaminated surface and Transfer Contamination” arelisted in Table 2:

TABLE 2 Materials C. sporogenes spores ATCC #3584, titer~1.0 × 10⁸CFU/mL (in water). 1x phosphate buffered saline with 0.05% TWEEN 20(“sampling solution”) Fetal bovine serum (“FBS”) 9 Medical gradestainless steel plates (304 grade), 12.7 cm by 18 cm 0.525% sodiumhypochlorite in water Isopropyl alcohol (“IPA”), 70% v/v in waterMILLI-Q deionized water Neutralizing broth (LETHEEN BROTH, obtained fromDifco, BD) Lab paper towels 1.5 mL centrifuge tubes 3M AC PETRIFILM,obtained from 3M Co., St. Paul, MN 3 polytetrafluoroethylene (“PTFE”)applicators (“dowel rods”) Snap-off swabs (CLEANTIPS Swabs) 50 mL FALCONtubes Heating block Wiping device (see FIGS. 4A-4B and the descriptionin step 9 below)

The “Test Method for Removal of Microorganisms from aMicroorganism-contaminated Surface and Transfer Contamination” wasperformed using the following protocol:

1) A stock solution of C. sporogenes spores (ATCC #3584) was titered onthe day of the experiment to ensure that the titer was about 1×10⁸CFU/mL.

2) An “inoculum solution” was prepared by pipetting 500 microliters ofFBS into 8.5 mL of distilled water to obtain a 9.0 mL of diluted FBSsolution, and then pipetting 1.0 mL of the spore stock into the dilutedFBS solution.

3) An “inoculum control sample” was prepared by pipetting 100microliters of the inoculum solution into a 50 mL conical tubecontaining 10 mL of LETHEEN broth (Difco, BD). The 50 mL conical tubewas sonicated for 1 minute and then vortexed for 1 minute. A 2 mLaliquot was removed and heat shocked for 10 minutes at 80° C. A 1 mLaliquot of the cells in neutralizing broth was pipetted onto a 3MPETRIFILM Aerobic Count (AC) plate. Next, a dilution series from 1:10 to1:100,000 of the cells in neutralizing broth was prepared using sterileButterfield's buffer (3M, 9 mL flip top tubes), and then 1 mL of eachdilution was plated onto appropriately labeled AC plates.

4) Step 3 was repeated two more times, to provide a total of n=3“inoculum control samples”.

5) Three “contaminated plates” were generated for verification ofmicroorganism recovery. The plates were contaminated by pipetting 100 mLof the inoculum solution onto each of three cleaned medical gradestainless steel plates (see the “Cleaning procedure for medical gradestainless steel plates”, below). The inoculum solution was spread overthe plates with PTFE dowels, and then was allowed to air dry.

Cleaning Procedure for Cleaning Medical Grade Stainless Steel Plates:

-   -   (a) About 5 mL of distilled water was pipette over the plates,        and the plates were wiped clean (all wiping was done with lab        paper towels);    -   (b) The plates were sprayed with a 1:10 dilution of household        bleach in water, and after 10 minutes the plates were wiped        clean;    -   (c) 5 mL of sterile distilled water was pipette onto the plates,        and the plates were wiped clean;    -   (d) The plates were sprayed with 70% IPA in water and        immediately wiped clean;    -   (e) The plates were again sprayed with 70% IPA in water and then        allowed to air dry; and    -   (f) The plates were autoclaved at 121° C. for 20 minutes.

6) To verify recovery of microorganisms from contaminated plates,“recovery verification control” samples were obtained using a “swabrecovery procedure” as described below:

Swab Recovery Procedure (Using a Single Swab for Each Plate):

-   -   (a) A snap-off swab was soaked in “sampling solution”;    -   (b) the plate surface was swabbed diagonally twice (back and        forth, switching sides of the swab between each direction);    -   (c) the plate surface was swabbed horizontally twice (back and        forth, switching sides of the swab between each direction); and    -   (d) the plate surface was swabbed vertically twice (back and        forth, switching sides of the swab between each direction).

The head of the swab was snapped off and placed into a 50 mL conicaltube containing 10 mL of neutralizing broth. The conical tube wassonicated for 1 minute in an ultrasonic bath, followed by 1 minute ofvortexing. A 2 mL aliquot was removed and heat shocked for 10 minutes at80° C. A 1 ml sample of cells in neutralizing broth was pipette onto a3M PETRIFILM AEROBIC COUNT (AC) plate. A dilution series from 1:10 to1:100,000 was prepared using sterile Butterfield's buffer (9 ml flip toptubes, available from 3M Co., St. Paul, Minn.,) and 1 ml of eachdilution was plated onto appropriately labeled AC plates. These were therecovery verification controls (n=3).

7) To assess the ability of a wipe to remove microorganisms from amicroorganism-contaminated surface, three more “contaminated plates”were generated (using cleaned medical grade stainless steel plates, andaccording to the details in Step 5 above).

8) A “wet wipe” sample was generated by loading with distilled andsterile water at desired loading weight (3.5× the weight of the drywipe). Loading technique included pipetting desired amount of deionizedH₂O onto the wipe, followed by gentle massaging to better incorporatethe water throughout the wipe. Wipes were weighed before and afterloading to ensure loading weight was correct.

9) The wet wipe was tested using a mechanical wiping device 400 (referto FIGS. 4A and 4B). The wet wipe 420 was locked onto the lever arm 450of the mechanical wiping device 400 using screw clamps 460. The leverarm 450 had a mass of about 350 g. The lever arm 450 with wet wipe 420attached was placed onto one of the contaminated plates (not shown) onplatform 410. The mechanical wiping device 400 was switched on, with thelever arm 450 operating at a rotational speed of about 100 rpm (seerotation arrow in FIG. 4B) to wipe the surface of contaminated plate for15 seconds, and the wet wipe 420 was then removed from the “wipedplate”. For each type of wipe, this step was repeated to give n=3 wipedplates.

10) Each of the “wiped plates” was then swabbed according to the detailsin Step 6 above, to generate “removal performance” samples (n=3).

11) “Transfer contamination” samples were generated by using the wipe ofStep 9, after wiping a contaminated plated, and while still attached tothe arm of the mechanical wiping device, to then wipe a clean plate (seeabove for “Cleaning procedure for cleaning medical grade stainless steelplates”) for 15 seconds at about 100 rpm. Theses wiped plates wereswabbed according the details in Step 6 above, to generate the “transfercontamination” samples (n=3).

12) For any additional wipe samples, Steps 8 to 11 were repeated.

13) All dilution plates were placed in an anaerobic incubator at 37° C.for about 24 hours.

14) The plates were subjected to counting of the microorganisms and thecounting data was analyzed using a log 10 difference between recoverycontrols and removal performance to calculate log reductions (LRV).

Calculation of Log Reduction Value (LRV) and Standard Deviation Values(S_(LR)):

A “log reduction value” (LRV) is a mathematical term used here torepresent the performance of a wipe in removing spores from a surface.LRV was calculated according to Equation (1) as the difference in themean log colony (MLC) forming units between the “recovery control”(MLC_(RC); this represents the initial spore population on the plates)and the remaining spores on a plate “after wiping” (MLC_(AW); thisrepresents the final spore population on the plates):

LRV=MLC_(RC)−MLC_(AW)  Equation (1):

A “percent removal” value for the percent removal of microorganisms froma plate after wiping could be calculated from the LRV according toEquation (2):

“percent removal”=100−10^((2-LRV))  Equation (2):

Thus, for example, an LRV of 3 would result in 100−10⁻¹, or 99.9, forthe corresponding percent removal value.

The variation for LRV (i.e., for LRV obtained according to Equation (1)above) was calculated as the “standard deviation of the LRV” (S_(LR)).Equation (3) shows the formula used to calculate S_(LR), where S_(RC)and SAW denote the standard deviation for MLC_(RC) (MLC recoverycontrol) and MLC_(AW) (MLC after wiping), respectively. The number ofreplicates for the recovery control and the spores remaining on thesurface of a plate after wiping was indicated by n_(RC) and n_(AW),respectively.

S _(LR)=[(S ² _(RC) /n _(RC))+(S ² _(AW) /n _(AW))]  Equation (3):

Calculation of Percent Transferred (PT):

In addition to the LRV, a percent transferred (PT) was calculated torepresent the transfer of spores from a contaminated wipe (i.e., a wipethat had contacted a contaminated surface) to a new, clean surface.First, the value for “total number of spores in the wipe” (W) wascalculated according to Equation (4) as the difference between thecolony forming units of the “initial spore population on the plate” (I)and the “spores remaining on the plate after wiping” (R).

W=I−R  Equation (4):

The “percent of spores transferred from the wipe to another surface”(PT) was then calculated according to Equation (5) (i.e., dividing the“spores recovered from a new surface after wiping with the contaminatedwipe” (T) by the “total number of spores in the wipe” (W) andmultiplying by 100).

PT=(T/W)*100  Equation (5):

Using the above “Test Method for Removal of Microorganisms from aMicroorganism-contaminated surface and Transfer Contamination”, resultsfor removal and cross-contamination of C. sporogenes ATCC #3584 sporesfrom surfaces using cationic polymer coated wipes were summarized as inTable 3.

The Experiments (Exp. 1 to Exp. 6) were listed in Table 3 to indicatewhich comparative examples and the examples were tested on the same day.

Abbreviations and notes in Table 3 include the following: BG-PEI=benzylguanylated PEI; C=control; Cel=a cellulose based nonwoven cloth;CelS=SCOTCH-BRITE ABSORBENT COUNTER CLOTH; CHG-PEI=chlorohexidinegluconate PEI; DA=poly(diacetoneacrylamide guanylhydrazone);DCHG-PEI=N,N′-dicyclohexyl guanylated PEI; Ex.=example; Exp.=experiment;G-PEI=guanylated PEI; LRV=log reduction value; NA=not available;PEI=poly(ethyleneimine); PET=poly(ethyleneterephthalate). Footnote “a”:recovery control is for an amount of spores recovered from surfacewithout wiping. Footnote “b”: Values are an average (n=3, unless notedotherwise). Footnote “c”: Standard deviations are listed in parenthesis(n=3, unless noted otherwise). Footnote “d”: values are an average forn=2.

TABLE 3 Spore transferred Wipe pre- from loaded Spores Percentcontaminated with water Recovery removed removal wipe to (X timescontrol^(a) from of spores another, clean Wipe Wipe Wipe weight of(Log₁₀ surface from surface Experiment Sample Coating Substrate wipe)cfu/plate) (LRV) surface (% transferred^(b)) Exp. 1 C1 None PET 3.5 6.011.39 95.93 3.85^(d) (0.06)^(c) (0.15)^(d) Exp. 1 Ex. 1 G-PEI PET 3.56.01 (0.06) 3.24 99.94 0.03 (0.12) Exp. 1 Ex. 2 DA PET 3.5 6.01 (0.06)3.47 99.97 0.01 (0.03) Exp. 2 C2 None PET 3.5 6.11 (0.09) 1.60 97.492.68 (0.12) Exp. 2 Ex.3 BG-PEI PET 3.5 6.11 (0.09) 2.58 99.74 0.04(0.33) Exp. 2 Ex. 4 CPB- PET 3.5 6.11 (0.09) 2.91 99.88 0.07 PEI (0.14)Exp. 3 C3 None PET 3.5 6.37 (0.05) 1.39 95.93 3.24 (0.03) Exp. 3 Ex. 5DCHG- PET 3.5 6.37 (0.05) 3.03 99.91 0.04 PEI (0.17) Exp. 4 C4 None PET3.5 6.12 (0.06) 2.51 99.69 0.42 (0.12) Exp. 4 C5 PEI PET 3.5 6.12 (0.06)2.38 99.58 0.22 (0.05) Exp. 4 Ex. 6 G-PEI PET 3.5 6.12 (0.06) 3.41 99.960.02 (0.13) Exp. 5 C6 None CelS 3.5 6.38 (0.05) 2.32 99.52 NA (0.08)Exp. 5 Ex. 7 G-PEI CelS 3.5 6.38 (0.05) 3.44 99.96 NA (0.20) Exp. 6 C7None Cel 4.5 6.28 (0.08) 1.64 97.71 NA (0.04) Exp. 6 Ex. 8 G-PEI Cel 4.56.28 (0.08) 2.59 99.74 NA (0.07)

Other modifications and variations to the present disclosure may bepracticed by those of ordinary skill in the art, without departing fromthe spirit and scope of the present disclosure. It is understood thataspects of the various embodiments may be interchanged in whole or partor combined with other aspects of the various embodiments. The precedingdescription, given in order to enable one of ordinary skill in the artto practice the claimed disclosure, is not to be construed as limitingthe scope of the disclosure, which is defined by the claims and allequivalents thereto.

What is claimed is:
 1. A wipe comprising: a substrate comprising asponge, a woven fabric, or a nonwoven fabric, wherein the substrate isflexible; a cationic coating disposed on a surface of the substrate,distributed throughout at least a portion of the substrate, or both, thecationic coating comprising a guanidinyl-containing polymer that iscovalently bonded to the substrate or both crosslinked on the substrateand covalently bonded to the substrate, wherein theguanidinyl-containing polymer is a reaction product of (a) a guanylatingagent and (b) a carbonyl-containing polymer precursor or anamino-containing polymer precursor; and a liquid comprising water, awater-miscible organic solvent, or a mixture thereof, wherein the liquidis present in an amount of 0.5 to 10 times of the weight of the wipewithout the liquid; wherein the wipe, when contacted in the presence ofa liquid with an area of a microorganism-contaminated surface, removesat least 99 percent of the microorganisms from the area, and wherein thewipe, when contacted in the presence of the liquid with the area of themicroorganism-contaminated surface and then contacted with a secondsurface, transfers no more than 0.2 percent of the microorganisms fromthe wipe to the second surface.
 2. The wipe according to claim 1,wherein the guanidinyl-containing polymer is of the Formula (I):

wherein: R¹ is hydrogen, C₁-C₁₂ (hetero)alkyl, a C₅-C₁₂ (hetero)aryl, ora residue of the polymer chain; R² is a covalent bond, a C₂ to C₁₂(hetero)alkylene, or a C₅-C₁₂ (hetero)arylene; R³ is hydrogen, C₁-C₁₂(hetero)alkyl, C₅-C₁₂ (hetero)aryl, or a residue of the polymer chainwhen n is 0; each R⁴ is independently hydrogen, C₁-C₁₂ (hetero)alkyl,C₅-C₁₂ (hetero)aryl; R⁵ is hydrogen, C₁-C₁₂ (hetero)alkyl, or C₅-C₁₂(hetero)aryl, or —N(R⁴)₂; n is 0 or 1; m is 1 or 2; and x is an integerequal to at least
 1. 3. The wipe according to claim 2, wherein theguanidinyl-containing polymer is of Formula (II):


4. The wipe according to claim 2, wherein the guanidinyl-containingpolymer is of Formula (IV):


5. The wipe according to claim 1, wherein the guanidinyl-containingpolymer is a reaction product of (a) a guanylating agent and (b) acarbonyl-containing polymer precursor, and wherein 1 to 90 mole percentof the carbonyl groups of the carbonyl-containing polymer precursor arereacted with the guanylating agent.
 6. The wipe according to claim 1,wherein the guanidinyl-containing polymer is a reaction product of (a) aguanylating agent and (b) a carbonyl-containing polymer precursor, andwherein the guanidinyl-containing polymer is crosslinked with aN,N′-(hetero)alkylenebis(meth)acrylamide.
 7. The wipe according to claim1, wherein the guanidinyl-containing polymer is a reaction product of a(a) guanylating agent and (b) an amino-containing polymer precursor, andwherein 1 to 90 mole percent of the amino groups of the amino-containingpolymer precursor are reacted with the guanylating agent.
 8. The wipeaccording to claim 1, wherein the guanidinyl-containing polymer is areaction product of (a) a guanylating agent and (b) an amino-containingpolymer, and wherein the guanidinyl-containing polymer is crosslinkedwith a polyglycidylether.
 9. The wipe according to claim 1, wherein theguanidinyl-containing polymer is present in an amount of 0.1 weightpercent to 10 weight percent based on a total weight of the wipe. 10.The wipe according to claim 1, wherein the liquid is present in anamount of 0.5 to 5 times of the weight of the wipe without the liquid.11. The wipe according to claim 1, wherein the liquid further comprisesa disinfectant.